Organic electroluminescent materials and devices

ABSTRACT

A compound including a first ligand L X  of Formula II 
     
       
         
         
             
             
         
       
     
     is disclosed, where F is a 5-membered or 6-membered carbocyclic or heterocyclic ring; each R F  and R G  independently represents mono to the maximum possible number of substitutions, or no substitution; Z 3  and Z 4  are each independently C or N and coordinated to a metal M to form a 5-membered chelate ring; G is a fused ring structure comprising five or more fused heterocyclic or carbocyclic rings, of which at least one ring is of Formula III 
     
       
         
         
             
             
         
       
     
     the fused heterocyclic or carbocyclic rings in the fused ring structure G are 5-membered or 6-membered; of which if two or more 5-membered rings are present, at least two of the 5-membered rings are fused to one another; Y can be one of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO 2 , CR′R″, SiR′R″, and GeR′R″; the metal M can be coordinated to other ligands; and the ligand L X  can be linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent application Ser. No. 16/594,384, filed on Oct. 7, 2019, which is a continuation-in-part of U.S. patent application Ser. No. 16/283,219, filed on Feb. 22, 2019, which is a continuation-in-part of U.S. patent application Ser. No. 16/235,390, filed on Dec. 28, 2018, which claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Application No. 62/643,472, filed on Mar. 15, 2018, to U.S. Provisional Application No. 62/641,644, filed on Mar. 12, 2018, and to U.S. Provisional Application No. 62/673,178, filed on May 18, 2018. U.S. patent application Ser. No. 16/594,384 also claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Application No. 62/754,879, filed on Nov. 2, 2018, the entire contents of which are incorporated herein by reference.

FIELD

The present disclosure generally relates to organometallic compounds and formulations and their various uses including as emitters in devices such as organic light emitting diodes and related electronic devices.

BACKGROUND

Opto-electronic devices that make use of organic materials are becoming increasingly desirable for various reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials.

OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting.

One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Alternatively, the OLED can be designed to emit white light. In conventional liquid crystal displays emission from a white backlight is filtered using absorption filters to produce red, green and blue emission. The same technique can also be used with OLEDs. The white OLED can be either a single emissive layer (EML) device or a stack structure. Color may be measured using CIE coordinates, which are well known to the art.

SUMMARY

In one aspect, the present disclosure provides a compound comprising a first ligand L_(X) of Formula II

is disclosed. In Formula II, F is a 5-membered or 6-membered carbocyclic or heterocyclic ring; each R^(F) and R^(G) independently represents mono to the maximum possible number of substitutions, or no substitution; Z³ and Z⁴ are each independently C or N and coordinated to a metal M to form a 5-membered chelate ring; G is a fused ring structure comprising five or more fused heterocyclic or carbocyclic rings, of which at least one ring is of Formula III

the fused heterocyclic or carbocyclic rings in the fused ring structure G are 5-membered or 6-membered; of which if two or more 5-membered rings are present, at least two of the 5-membered rings are fused to one another; Y is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″; each R′, R″, R^(F), and R^(G) is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; the metal M can be coordinated to other ligands; and the ligand L_(X) can be linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand.

In another aspect, the present disclosure provides a formulation of the compound as described herein.

In yet another aspect, the present disclosure provides an OLED comprising an organic layer that comprises the compound as described herein.

In yet another aspect, the present disclosure provides a consumer product comprising an OLED with an organic layer comprising the compound as described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an organic light emitting device.

FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.

DETAILED DESCRIPTION A. Terminology

Unless otherwise specified, the below terms used herein are defined as follows:

As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.

As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.

As used herein, “solution processable” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.

A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.

As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.

As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.

The terms “halo,” “halogen,” and “halide” are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

The term “acyl” refers to a substituted carbonyl radical (C(O)—R_(s)).

The term “ester” refers to a substituted oxycarbonyl (—O—C(O)—R_(s) or —C(O)—O—R_(s)) radical.

The term “ether” refers to an —OR_(s) radical.

The terms “sulfanyl” or “thio-ether” are used interchangeably and refer to a —SR_(s) radical.

The term “sulfinyl” refers to a —S(O)—R_(s) radical.

The term “sulfonyl” refers to a —SO₂—R_(s) radical.

The term “phosphino” refers to a —P(R_(s))₃ radical, wherein each R_(s) can be same or different.

The term “silyl” refers to a —Si(R_(s))₃ radical, wherein each R_(s) can be same or different.

The term “boryl” refers to a —B(R_(s))₂ radical or its Lewis adduct —B(R_(s))₃ radical, wherein R_(s) can be same or different.

In each of the above, R_(s) can be hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combination thereof. Preferred R_(s) is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combination thereof.

The term “alkyl” refers to and includes both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group may be optionally substituted.

The term “cycloalkyl” refers to and includes monocyclic, polycyclic, and spiro alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. Additionally, the cycloalkyl group may be optionally substituted.

The terms “heteroalkyl” or “heterocycloalkyl” refer to an alkyl or a cycloalkyl radical, respectively, having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si and Se, preferably, O, S or N. Additionally, the heteroalkyl or heterocycloalkyl group may be optionally substituted.

The term “alkenyl” refers to and includes both straight and branched chain alkene radicals. Alkenyl groups are essentially alkyl groups that include at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyl groups are essentially cycloalkyl groups that include at least one carbon-carbon double bond in the cycloalkyl ring. The term “heteroalkenyl” as used herein refers to an alkenyl radical having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl group may be optionally substituted.

The term “alkynyl” refers to and includes both straight and branched chain alkyne radicals. Alkynyl groups are essentially alkyl groups that include at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted.

The terms “aralkyl” or “arylalkyl” are used interchangeably and refer to an alkyl group that is substituted with an aryl group. Additionally, the aralkyl group may be optionally substituted.

The term “heterocyclic group” refers to and includes aromatic and non-aromatic cyclic radicals containing at least one heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Hetero-aromatic cyclic radicals may be used interchangeably with heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperidino, pyrrolidino, and the like, and cyclic ethers/thio-ethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. Additionally, the heterocyclic group may be optionally substituted.

The term “aryl” refers to and includes both single-ring aromatic hydrocarbyl groups and polycyclic aromatic ring systems. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is an aromatic hydrocarbyl group, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Especially preferred is an aryl group having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may be optionally substituted.

The term “heteroaryl” refers to and includes both single-ring aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. The heteroatoms include, but are not limited to O, S, N, P, B, Si, and Se. In many instances, O, S, or N are the preferred heteroatoms. Hetero-single ring aromatic systems are preferably single rings with 5 or 6 ring atoms, and the ring can have from one to six heteroatoms. The hetero-polycyclic ring systems can have two or more rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. The hetero-polycyclic aromatic ring systems can have from one to six heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted.

Of the aryl and heteroaryl groups listed above, the groups of triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, and the respective aza-analogs of each thereof are of particular interest.

The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl, as used herein, are independently unsubstituted, or independently substituted, with one or more general substituents.

In many instances, the general substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof.

In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinations thereof.

In some instances, the more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, sulfanyl, and combinations thereof.

In yet other instances, the most preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

The terms “substituted” and “substitution” refer to a substituent other than H that is bonded to the relevant position, e.g., a carbon or nitrogen. For example, when R¹ represents mono-substitution, then one R¹ must be other than H (i.e., a substitution). Similarly, when R¹ represents di-substitution, then two of R¹ must be other than H. Similarly, when R¹ represents zero or no substitution, R¹, for example, can be a hydrogen for available valencies of ring atoms, as in carbon atoms for benzene and the nitrogen atom in pyrrole, or simply represents nothing for ring atoms with fully filled valencies, e.g., the nitrogen atom in pyridine. The maximum number of substitutions possible in a ring structure will depend on the total number of available valencies in the ring atoms.

As used herein, “combinations thereof” indicates that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can envision from the applicable list. For example, an alkyl and deuterium can be combined to form a partial or fully deuterated alkyl group; a halogen and alkyl can be combined to form a halogenated alkyl substituent; and a halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl. In one instance, the term substitution includes a combination of two to four of the listed groups. In another instance, the term substitution includes a combination of two to three groups. In yet another instance, the term substitution includes a combination of two groups. Preferred combinations of substituent groups are those that contain up to fifty atoms that are not hydrogen or deuterium, or those which include up to forty atoms that are not hydrogen or deuterium, or those that include up to thirty atoms that are not hydrogen or deuterium. In many instances, a preferred combination of substituent groups will include up to twenty atoms that are not hydrogen or deuterium.

The “aza” designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C—H groups in the respective aromatic ring can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.

As used herein, “deuterium” refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Pat. No. 8,557,400, Patent Pub. No. WO 2006/095951, and U.S. Pat. Application Pub. No. US 2011/0037057, which are hereby incorporated by reference in their entireties, describe the making of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan, et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65, which are incorporated by reference in their entireties, describe the deuteration of the methylene hydrogens in benzyl amines and efficient pathways to replace aromatic ring hydrogens with deuterium, respectively.

It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.

In some instance, a pair of adjacent substituents can be optionally joined or fused into a ring. The preferred ring is a five, six, or seven-membered carbocyclic or heterocyclic ring, includes both instances where the portion of the ring formed by the pair of substituents is saturated and where the portion of the ring formed by the pair of substituents is unsaturated. As used herein, “adjacent” means that the two substituents involved can be on the same ring next to each other, or on two neighboring rings having the two closest available substitutable positions, such as 2, 2′ positions in a biphenyl, or 1, 8 position in a naphthalene, as long as they can form a stable fused ring system.

B. The Compounds of the Present Disclosure

In one aspect, the present disclosure provides a compound comprising a first ligand L_(X) of Formula II

is disclosed. In Formula II, F is a 5-membered or 6-membered carbocyclic or heterocyclic ring; each R^(F) and R^(G) independently represents mono to the maximum possible number of substitutions, or no substitution; Z³ and Z⁴ are each independently C or N and coordinated to a metal M to form a 5-membered chelate ring; G is a fused ring structure comprising five or more fused heterocyclic or carbocyclic rings, of which at least one ring is of Formula III

the fused heterocyclic or carbocyclic rings in the fused ring structure G are 5-membered or 6-membered; of which if two or more 5-membered rings are present, at least two of the 5-membered rings are fused to one another; Y is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″; each R′, R″, R^(F), and R^(G) is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; the metal M can be coordinated to other ligands; and the ligand L_(X) can be linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand.

In some embodiments of the compound, the ligand L_(X) has a structure of Formula IV

where, A¹ to A⁴ are each independently C or N; one of A¹ to A⁴ is Z⁴ in Formula II; R^(H) and R^(I) represents mono to the maximum possibly number of substitutions, or no substitution; ring H is a 5-membered or 6-membered aromatic ring; n is 0 or 1; when n is 0, A⁸ is not present, two adjacent atoms of A⁵ to A⁷ are C, and the remaining atom of A⁵ to A⁷ is selected from the group consisting of NR′, O, S, and Se; when n is 1, two adjacent of A⁵ to A⁸ are C, and the remaining atoms of A⁵ to A⁸ are selected from the group consisting of C and N, and adjacent substituents of R^(H) and R^(I) join or fuse together to form at least two fused heterocyclic or carbocyclic rings; R′ and each R^(H) and R^(I) is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and any two substituents can be joined or fused together to form a ring.

In some embodiments of the compound whose ligand L_(X) has the structure of Formula IV, each R^(F), R^(H), and R^(I) is independently a hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein. In some embodiments, the metal M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Au, and Cu. In some embodiments, Y is O.

In some embodiments of the compound whose ligand L_(X) has the structure of Formula IV, n is 1. In some embodiments, n is 1, A⁵ to A⁸ are each C, a first 6-membered ring is fused to A⁵ and A⁶, and a second 6-membered ring is fused to the first 6-membered ring but not ring H. In some embodiments, the ring F is selected from the group consisting of pyridine, pyrimidine, pyrazine, imidazole, pyrazole, and N-heterocyclic carbene.

In some embodiments of the compound whose ligand L_(X) has the structure of Formula IV, the first ligand L_(X) is selected from the group consisting of:

where, Z⁷ to Z¹⁴ and, when present, Z¹⁵ to Z¹⁸ are each independently N or CR^(Q); each R^(Q) is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, and combinations thereof; and any two substituents may be joined or fused together to form a ring.

In some embodiments of the compound whose ligand L_(X) has the structure of Formula IV, the first ligand L_(X) is selected from the group consisting of L_(X1-1) to L_(X897-38) with the general numbering formula L_(Xh-m), and L_(X1-39) to L_(X1446-57) with the general numbering formula L_(Xi-n);

where h is an integer from 1 to 897, i is an integer from 1 to 1446, m is an integer from 1 to 38 referring to Structure 1 to Structure 38, and n is an integer from 39 to 57 referring to Structure 39 to Structure 57;

where for each L_(Xh-m); L_(Xh-1) (h=1 to 897) is based on Structure 1,

L_(Xh-2) (h=1 to 897) is based on Structure 2,

L_(Xh-3) (h=1 to 897) is based on Structure 3,

L_(Xh-4) (h=1 to 897) is based on Structure 4,

L_(Xh-5) (h=1 to 897) is based on Structure 5,

L_(Xh-6) (h=1 to 897) is based on Structure 6,

L_(Xh-7) (h=1 to 897) is based on Structure 7,

L_(Xh-8) (h=1 to 897) is based on Structure 8,

L_(Xh-9) (h=1 to 897) is based on Structure 9,

L_(Xh-10) (h=1 to 897) is based on Structure 10,

L_(Xh-11) (h=1 to 897) is based on Structure 11,

L_(Xh-12) (h=1 to 897) is based on Structure 12,

L_(Xh-13) (h=1 to 897) is based on Structure 13,

L_(Xh-14) (h=1 to 897) is based on Structure 14,

L_(Xh-15) (h=1 to 897) is based on Structure 15,

L_(Xh-16) (h=1 to 897) is based on Structure 16,

L_(Xh-17) (h=1 to 897) is based on Structure 17,

L_(Xh-18) (h=1 to 897) is based on Structure 18,

L_(Xh-19) (h=1 to 897) is based on Structure 19,

L_(Xh-20) (h=1 to 897) is based on Structure 20,

L_(Xh-21) (h=1 to 897) is based on Structure 21,

L_(Xh-22) (h=1 to 897) is based on Structure 22,

L_(Xh-23) (h=1 to 897) is based on Structure 23,

L_(Xh-24) (h=1 to 897) is based on Structure 24,

L_(Xh-25) (h=1 to 897) is based on Structure 25,

L_(Xh-26) (h=1 to 897) is based on Structure 26,

L_(Xh-27) (h=1 to 897) is based on Structure 27,

L_(Xh-28) (h=1 to 897) is based on Structure 28,

L_(Xh-29) (h=1 to 897) is based on Structure 29,

L_(Xh-30) (h=1 to 897) is based on Structure 30,

L_(Xh-31) (h=1 to 897) is based on Structure 31,

L_(Xh-32) (h=1 to 897) is based on Structure 32,

L_(Xh-33) (h=1 to 897) is based on Structure 33,

L_(Xh-34) (h=1 to 897) is based on Structure 34,

L_(Xh-35) (h=1 to 897) is based on Structure 35,

L_(Xh-36) (h=1 to 897) is based on Structure 36,

L_(Xh-37) (h=1 to 897) is based on Structure 37,

L_(Xh-38) (h=1 to 897) is based on Structure 38,

where for each h, R^(E), R^(F), and Y are defined as below:

h R^(E) R^(F) h R^(E) R^(F) h R^(E) R^(F) h R^(E) R^(F) 1 R¹ R¹  226 R⁴ R¹⁹ 451 R⁷  R³⁷ 676 R³³ R⁵⁵ 2 R¹ R²  227 R⁴ R²⁰ 452 R⁷  R³⁸ 677 R³³ R⁵⁶ 3 R¹ R³  228 R⁴ R²¹ 453 R⁷  R³⁹ 678 R³³ R⁵⁷ 4 R¹ R⁴  229 R⁴ R²² 454 R⁷  R⁴⁰ 679 R³³ R⁵⁸ 5 R¹ R⁵  230 R⁴ R²³ 455 R⁷  R⁴¹ 680 R³³ R⁵⁹ 6 R¹ R⁶  231 R⁴ R²⁴ 456 R⁷  R⁴² 681 R³³ R⁶⁰ 7 R¹ R⁷  232 R⁴ R²⁵ 457 R⁷  R⁴³ 682 R³³ R⁶¹ 8 R¹ R⁸  233 R⁴ R²⁶ 458 R⁷  R⁴⁴ 683 R³³ R⁶² 9 R¹ R⁹  234 R⁴ R²⁷ 459 R⁷  R⁴⁵ 684 R³³ R⁶³ 10 R¹ R¹⁰ 235 R⁴ R²⁸ 460 R⁷  R⁴⁶ 685 R³³ R⁶⁴ 11 R¹ R¹¹ 236 R⁴ R²⁹ 461 R⁷  R⁴⁷ 686 R³³ R⁶⁵ 12 R¹ R¹² 237 R⁴ R³⁰ 462 R⁷  R⁴⁸ 687 R³³ R⁶⁶ 13 R¹ R¹³ 238 R⁴ R³¹ 463 R⁷  R⁴⁹ 688 R³³ R⁶⁷ 14 R¹ R¹⁴ 239 R⁴ R³² 464 R⁷  R⁵⁰ 689 R³³ R⁶⁸ 15 R¹ R¹⁵ 240 R⁴ R³³ 465 R⁷  R⁵¹ 690 R³³ R⁶⁹ 16 R¹ R¹⁶ 241 R⁴ R³⁴ 466 R⁷  R⁵² 691 R³⁴ R¹  17 R¹ R¹⁷ 242 R⁴ R³⁵ 467 R⁷  R⁵³ 692 R³⁴ R²  18 R¹ R¹⁸ 243 R⁴ R³⁶ 468 R⁷  R⁵⁴ 693 R³⁴ R³  19 R¹ R¹⁹ 244 R⁴ R³⁷ 469 R⁷  R⁵⁵ 694 R³⁴ R⁴  20 R¹ R²⁰ 245 R⁴ R³⁸ 470 R⁷  R⁵⁶ 695 R³⁴ R⁵  21 R¹ R²¹ 246 R⁴ R³⁹ 471 R⁷  R⁵⁷ 696 R³⁴ R⁶  22 R¹ R²² 247 R⁴ R⁴⁰ 472 R⁷  R⁵⁸ 697 R³⁴ R⁷  23 R¹ R²³ 248 R⁴ R⁴¹ 473 R⁷  R⁵⁹ 698 R³⁴ R⁸  24 R¹ R²⁴ 249 R⁴ R⁴² 474 R⁷  R⁶⁰ 699 R³⁴ R⁹  25 R¹ R²⁵ 250 R⁴ R⁴³ 475 R⁷  R⁶¹ 700 R³⁴ R¹⁰ 26 R¹ R²⁶ 251 R⁴ R⁴⁴ 476 R⁷  R⁶² 701 R³⁴ R¹¹ 27 R¹ R²⁷ 252 R⁴ R⁴⁵ 477 R⁷  R⁶³ 702 R³⁴ R¹² 28 R¹ R²⁸ 253 R⁴ R⁴⁶ 478 R⁷  R⁶⁴ 703 R³⁴ R¹³ 29 R¹ R²⁹ 254 R⁴ R⁴⁷ 479 R⁷  R⁶⁵ 704 R³⁴ R¹⁴ 30 R¹ R³⁰ 255 R⁴ R⁴⁸ 480 R⁷  R⁶⁶ 705 R³⁴ R¹⁵ 31 R¹ R³¹ 256 R⁴ R⁴⁹ 481 R⁷  R⁶⁷ 706 R³⁴ R¹⁶ 32 R¹ R³² 257 R⁴ R⁵⁰ 482 R⁷  R⁶⁸ 707 R³⁴ R¹⁷ 33 R¹ R³³ 258 R⁴ R⁵¹ 483 R⁷  R⁶⁹ 708 R³⁴ R¹⁸ 34 R¹ R³⁴ 259 R⁴ R⁵² 484 R³⁰ R¹  709 R³⁴ R¹⁹ 35 R¹ R³⁵ 260 R⁴ R⁵³ 485 R³⁰ R²  710 R³⁴ R²⁰ 36 R¹ R³⁶ 261 R⁴ R⁵⁴ 486 R³⁰ R³  711 R³⁴ R²¹ 37 R¹ R³⁷ 262 R⁴ R⁵⁵ 487 R³⁰ R⁴  712 R³⁴ R²² 38 R¹ R³⁸ 263 R⁴ R⁵⁶ 488 R³⁰ R⁵  713 R³⁴ R²³ 39 R¹ R³⁹ 264 R⁴ R⁵⁷ 489 R³⁰ R⁶  714 R³⁴ R²⁴ 40 R¹ R⁴⁰ 265 R⁴ R⁵⁸ 490 R³⁰ R⁷  715 R³⁴ R²⁵ 41 R¹ R⁴¹ 266 R⁴ R⁵⁹ 491 R³⁰ R⁸  716 R³⁴ R²⁶ 42 R¹ R⁴² 267 R⁴ R⁶⁰ 492 R³⁰ R⁹  717 R³⁴ R²⁷ 43 R¹ R⁴³ 268 R⁴ R⁶¹ 493 R³⁰ R¹⁰ 718 R³⁴ R²⁸ 44 R¹ R⁴⁴ 269 R⁴ R⁶² 494 R³⁰ R¹¹ 719 R³⁴ R²⁹ 45 R¹ R⁴⁵ 270 R⁴ R⁶³ 495 R³⁰ R¹² 720 R³⁴ R³⁰ 46 R¹ R⁴⁶ 271 R⁴ R⁶⁴ 496 R³⁰ R¹³ 721 R³⁴ R³¹ 47 R¹ R⁴⁷ 272 R⁴ R⁶⁵ 497 R³⁰ R¹⁴ 722 R³⁴ R³² 48 R¹ R⁴⁸ 273 R⁴ R⁶⁶ 498 R³⁰ R¹⁵ 723 R³⁴ R³³ 49 R¹ R⁴⁹ 274 R⁴ R⁶⁷ 499 R³⁰ R¹⁶ 724 R³⁴ R³⁴ 50 R¹ R⁵⁰ 275 R⁴ R⁶⁸ 500 R³⁰ R¹⁷ 725 R³⁴ R³⁵ 51 R¹ R⁵¹ 276 R⁴ R⁶⁹ 501 R³⁰ R¹⁸ 726 R³⁴ R³⁶ 52 R¹ R⁵² 277 R⁵ R¹  502 R³⁰ R¹⁹ 727 R³⁴ R³⁷ 53 R¹ R⁵³ 278 R⁵ R²  503 R³⁰ R²⁰ 728 R³⁴ R³⁸ 54 R¹ R⁵⁴ 279 R⁵ R³  504 R³⁰ R²¹ 729 R³⁴ R³⁹ 55 R¹ R⁵⁵ 280 R⁵ R⁴  505 R³⁰ R²² 730 R³⁴ R⁴⁰ 56 R¹ R⁵⁶ 281 R⁵ R⁵  506 R³⁰ R²³ 731 R³⁴ R⁴¹ 57 R¹ R⁵⁷ 282 R⁵ R⁶  507 R³⁰ R²⁴ 732 R³⁴ R⁴² 58 R¹ R⁵⁸ 283 R⁵ R⁷  508 R³⁰ R²⁵ 733 R³⁴ R⁴³ 59 R¹ R⁵⁹ 284 R⁵ R⁸  509 R³⁰ R²⁶ 734 R³⁴ R⁴⁴ 60 R¹ R⁶⁰ 285 R⁵ R⁹  510 R³⁰ R²⁷ 735 R³⁴ R⁴⁵ 61 R¹ R⁶¹ 286 R⁵ R¹⁰ 511 R³⁰ R²⁸ 736 R³⁴ R⁴⁶ 62 R¹ R⁶² 287 R⁵ R¹¹ 512 R³⁰ R²⁹ 737 R³⁴ R⁴⁷ 63 R¹ R⁶³ 288 R⁵ R¹² 513 R³⁰ R³⁰ 738 R³⁴ R⁴⁸ 64 R¹ R⁶⁴ 289 R⁵ R¹³ 514 R³⁰ R³¹ 739 R³⁴ R⁴⁹ 65 R¹ R⁶⁵ 290 R⁵ R¹⁴ 515 R³⁰ R³² 740 R³⁴ R⁵⁰ 66 R¹ R⁶⁶ 291 R⁵ R¹⁵ 516 R³⁰ R³³ 741 R³⁴ R⁵¹ 67 R¹ R⁶⁷ 292 R⁵ R¹⁶ 517 R³⁰ R³⁴ 742 R³⁴ R⁵² 68 R¹ R⁶⁸ 293 R⁵ R¹⁷ 518 R³⁰ R³⁵ 743 R³⁴ R⁵³ 69 R¹ R⁶⁹ 294 R⁵ R¹⁸ 519 R³⁰ R³⁶ 744 R³⁴ R⁵⁴ 70 R² R¹  295 R⁵ R¹⁹ 520 R³⁰ R³⁷ 745 R³⁴ R⁵⁵ 71 R² R²  296 R⁵ R²⁰ 521 R³⁰ R³⁸ 746 R³⁴ R⁵⁶ 72 R² R³  297 R⁵ R²¹ 522 R³⁰ R³⁹ 747 R³⁴ R⁵⁷ 73 R² R⁴  298 R⁵ R²² 523 R³⁰ R⁴⁰ 748 R³⁴ R⁵⁸ 74 R² R⁵  299 R⁵ R²³ 524 R³⁰ R⁴¹ 749 R³⁴ R⁵⁹ 75 R² R⁶  300 R⁵ R²⁴ 525 R³⁰ R⁴² 750 R³⁴ R⁶⁰ 76 R² R⁷  301 R⁵ R²⁵ 526 R³⁰ R⁴³ 751 R³⁴ R⁶¹ 77 R² R⁸  302 R⁵ R²⁶ 527 R³⁰ R⁴⁴ 752 R³⁴ R⁶² 78 R² R⁹  303 R⁵ R²⁷ 528 R³⁰ R⁴⁵ 753 R³⁴ R⁶³ 79 R² R¹⁰ 304 R⁵ R²⁸ 529 R³⁰ R⁴⁶ 754 R³⁴ R⁶⁴ 80 R² R¹¹ 305 R⁵ R²⁹ 530 R³⁰ R⁴⁷ 755 R³⁴ R⁶⁵ 81 R² R¹² 306 R⁵ R³⁰ 531 R³⁰ R⁴⁸ 756 R³⁴ R⁶⁶ 82 R² R¹³ 307 R⁵ R³¹ 532 R³⁰ R⁴⁹ 757 R³⁴ R⁶⁷ 83 R² R¹⁴ 308 R⁵ R³² 533 R³⁰ R⁵⁰ 758 R³⁴ R⁶⁸ 84 R² R¹⁵ 309 R⁵ R³³ 534 R³⁰ R⁵¹ 759 R³⁴ R⁶⁹ 85 R² R¹⁶ 310 R⁵ R³⁴ 535 R³⁰ R⁵² 760 R³⁵ R¹  86 R² R¹⁷ 311 R⁵ R³⁵ 536 R³⁰ R⁵³ 761 R³⁵ R²  87 R² R¹⁸ 312 R⁵ R³⁶ 537 R³⁰ R⁵⁴ 762 R³⁵ R³  88 R² R¹⁹ 313 R⁵ R³⁷ 538 R³⁰ R⁵⁵ 763 R³⁵ R⁴  89 R² R²⁰ 314 R⁵ R³⁸ 539 R³⁰ R⁵⁶ 764 R³⁵ R⁵  90 R² R²¹ 315 R⁵ R³⁹ 540 R³⁰ R⁵⁷ 765 R³⁵ R⁶  91 R² R²² 316 R⁵ R⁴⁰ 541 R³⁰ R⁵⁸ 766 R³⁵ R⁷  92 R² R²³ 317 R⁵ R⁴¹ 542 R³⁰ R⁵⁹ 767 R³⁵ R⁸  93 R² R²⁴ 318 R⁵ R⁴² 543 R³⁰ R⁶⁰ 768 R³⁵ R⁹  94 R² R²⁵ 319 R⁵ R⁴³ 544 R³⁰ R⁶¹ 769 R³⁵ R¹⁰ 95 R² R²⁶ 320 R⁵ R⁴⁴ 545 R³⁰ R⁶² 770 R³⁵ R¹¹ 96 R² R²⁷ 321 R⁵ R⁴⁵ 546 R³⁰ R⁶³ 771 R³⁵ R¹² 97 R² R²⁸ 322 R⁵ R⁴⁶ 547 R³⁰ R⁶⁴ 772 R³⁵ R¹³ 98 R² R²⁹ 323 R⁵ R⁴⁷ 548 R³⁰ R⁶⁵ 773 R³⁵ R¹⁴ 99 R² R³⁰ 324 R⁵ R⁴⁸ 549 R³⁰ R⁶⁶ 774 R³⁵ R¹⁵ 100 R² R³¹ 325 R⁵ R⁴⁹ 550 R³⁰ R⁶⁷ 775 R³⁵ R¹⁶ 101 R² R³² 326 R⁵ R⁵⁰ 551 R³⁰ R⁶⁸ 776 R³⁵ R¹⁷ 102 R² R³³ 327 R⁵ R⁵¹ 552 R³⁰ R⁶⁹ 777 R³⁵ R¹⁸ 103 R² R³⁴ 328 R⁵ R⁵² 553 R³² R¹  778 R³⁵ R¹⁹ 104 R² R³⁵ 329 R⁵ R⁵³ 554 R³² R²  779 R³⁵ R²⁰ 105 R² R³⁶ 330 R⁵ R⁵⁴ 555 R³² R³  780 R³⁵ R²¹ 106 R² R³⁷ 331 R⁵ R⁵⁵ 556 R³² R⁴  781 R³⁵ R²² 107 R² R³⁸ 332 R⁵ R⁵⁶ 557 R³² R⁵  782 R³⁵ R²³ 108 R² R³⁹ 333 R⁵ R⁵⁷ 558 R³² R⁶  783 R³⁵ R²⁴ 109 R² R⁴⁰ 334 R⁵ R⁵⁸ 559 R³² R⁷  784 R³⁵ R²⁵ 110 R² R⁴¹ 335 R⁵ R⁵⁹ 560 R³² R⁸  785 R³⁵ R²⁶ 111 R² R⁴² 336 R⁵ R⁶⁰ 561 R³² R⁹  786 R³⁵ R²⁷ 112 R² R⁴³ 337 R⁵ R⁶¹ 562 R³² R¹⁰ 787 R³⁵ R²⁸ 113 R² R⁴⁴ 338 R⁵ R⁶² 563 R³² R¹¹ 788 R³⁵ R²⁹ 114 R² R⁴⁵ 339 R⁵ R⁶³ 564 R³² R¹² 789 R³⁵ R³⁰ 115 R² R⁴⁶ 340 R⁵ R⁶⁴ 565 R³² R¹³ 790 R³⁵ R³¹ 116 R² R⁴⁷ 341 R⁵ R⁶⁵ 566 R³² R¹⁴ 791 R³⁵ R³² 117 R² R⁴⁸ 342 R⁵ R⁶⁶ 567 R³² R¹⁵ 792 R³⁵ R³³ 118 R² R⁴⁹ 343 R⁵ R⁶⁷ 568 R³² R¹⁶ 793 R³⁵ R³⁴ 119 R² R⁵⁰ 344 R⁵ R⁶⁸ 569 R³² R¹⁷ 794 R³⁵ R³⁵ 120 R² R⁵¹ 345 R⁵ R⁶⁹ 570 R³² R¹⁸ 795 R³⁵ R³⁶ 121 R² R⁵² 346 R⁶ R¹  571 R³² R¹⁹ 796 R³⁵ R³⁷ 122 R² R⁵³ 347 R⁶ R²  572 R³² R²⁰ 797 R³⁵ R³⁸ 123 R² R⁵⁴ 348 R⁶ R³  573 R³² R²¹ 798 R³⁵ R³⁹ 124 R² R⁵⁵ 349 R⁶ R⁴  574 R³² R²² 799 R³⁵ R⁴⁰ 125 R² R⁵⁶ 350 R⁶ R⁵  575 R³² R²³ 800 R³⁵ R⁴¹ 126 R² R⁵⁷ 351 R⁶ R⁶  576 R³² R²⁴ 801 R³⁵ R⁴² 127 R² R⁵⁸ 352 R⁶ R⁷  577 R³² R²⁵ 802 R³⁵ R⁴³ 128 R² R⁵⁹ 353 R⁶ R⁸  578 R³² R²⁶ 803 R³⁵ R⁴⁴ 129 R² R⁶⁰ 354 R⁶ R⁹  579 R³² R²⁷ 804 R³⁵ R⁴⁵ 130 R² R⁶¹ 355 R⁶ R¹⁰ 580 R³² R²⁸ 805 R³⁵ R⁴⁶ 131 R² R⁶² 356 R⁶ R¹¹ 581 R³² R²⁹ 806 R³⁵ R⁴⁷ 132 R² R⁶³ 357 R⁶ R¹² 582 R³² R³⁰ 807 R³⁵ R⁴⁸ 133 R² R⁶⁴ 358 R⁶ R¹³ 583 R³² R³¹ 808 R³⁵ R⁴⁹ 134 R² R⁶⁵ 359 R⁶ R¹⁴ 584 R³² R³² 809 R³⁵ R⁵⁰ 135 R² R⁶⁶ 360 R⁶ R¹⁵ 585 R³² R³³ 810 R³⁵ R⁵¹ 136 R² R⁶⁷ 361 R⁶ R¹⁶ 586 R³² R³⁴ 811 R³⁵ R⁵² 137 R² R⁶⁸ 362 R⁶ R¹⁷ 587 R³² R³⁵ 812 R³⁵ R⁵³ 138 R² R⁶⁹ 363 R⁶ R¹⁸ 588 R³² R³⁶ 813 R³⁵ R⁵⁴ 139 R³ R¹  364 R⁶ R¹⁹ 589 R³² R³⁷ 814 R³⁵ R⁵⁵ 140 R³ R²  365 R⁶ R²⁰ 590 R³² R³⁸ 815 R³⁵ R⁵⁶ 141 R³ R³  366 R⁶ R²¹ 591 R³² R³⁹ 816 R³⁵ R⁵⁷ 142 R³ R⁴  367 R⁶ R²² 592 R³² R⁴⁰ 817 R³⁵ R⁵⁸ 143 R³ R⁵  368 R⁶ R²³ 593 R³² R⁴¹ 818 R³⁵ R⁵⁹ 144 R³ R⁶  369 R⁶ R²⁴ 594 R³² R⁴² 819 R³⁵ R⁶⁰ 145 R³ R⁷  370 R⁶ R²⁵ 595 R³² R⁴³ 820 R³⁵ R⁶¹ 146 R³ R⁸  371 R⁶ R²⁶ 596 R³² R⁴⁴ 821 R³⁵ R⁶² 147 R³ R⁹  372 R⁶ R²⁷ 597 R³² R⁴⁵ 822 R³⁵ R⁶³ 148 R³ R¹⁰ 373 R⁶ R²⁸ 598 R³² R⁴⁶ 823 R³⁵ R⁶⁴ 149 R³ R¹¹ 374 R⁶ R²⁹ 599 R³² R⁴⁷ 824 R³⁵ R⁶⁵ 150 R³ R¹² 375 R⁶ R³⁰ 600 R³² R⁴⁸ 825 R³⁵ R⁶⁶ 151 R³ R¹³ 376 R⁶ R³¹ 601 R³² R⁴⁹ 826 R³⁵ R⁶⁷ 152 R³ R¹⁴ 377 R⁶ R³² 602 R³² R⁵⁰ 827 R³⁵ R⁶⁸ 153 R³ R¹⁵ 378 R⁶ R³³ 603 R³² R⁵¹ 828 R³⁵ R⁶⁹ 154 R³ R¹⁶ 379 R⁶ R³⁴ 604 R³² R⁵² 829 R³⁶ R¹  155 R³ R¹⁷ 380 R⁶ R³⁵ 605 R³² R⁵³ 830 R³⁶ R²  156 R³ R¹⁸ 381 R⁶ R³⁶ 606 R³² R⁵⁴ 831 R³⁶ R³  157 R³ R¹⁹ 382 R⁶ R³⁷ 607 R³² R⁵⁵ 832 R³⁶ R⁴  158 R³ R²⁰ 383 R⁶ R³⁸ 608 R³² R⁵⁶ 833 R³⁶ R⁵  159 R³ R²¹ 384 R⁶ R³⁹ 609 R³² R⁵⁷ 834 R³⁶ R⁶  160 R³ R²² 385 R⁶ R⁴⁰ 610 R³² R⁵⁸ 835 R³⁶ R⁷  161 R³ R²³ 386 R⁶ R⁴¹ 611 R³² R⁵⁹ 836 R³⁶ R⁸  162 R³ R²⁴ 387 R⁶ R⁴² 612 R³² R⁶⁰ 837 R³⁶ R⁹  163 R³ R²⁵ 388 R⁶ R⁴³ 613 R³² R⁶¹ 838 R³⁶ R¹⁰ 164 R³ R²⁶ 389 R⁶ R⁴⁴ 614 R³² R⁶² 839 R³⁶ R¹¹ 165 R³ R²⁷ 390 R⁶ R⁴⁵ 615 R³² R⁶³ 840 R³⁶ R¹² 166 R³ R²⁸ 391 R⁶ R⁴⁶ 616 R³² R⁶⁴ 841 R³⁶ R¹³ 167 R³ R²⁹ 392 R⁶ R⁴⁷ 617 R³² R⁶⁵ 842 R³⁶ R¹⁴ 168 R³ R³⁰ 393 R⁶ R⁴⁸ 618 R³² R⁶⁶ 843 R³⁶ R¹⁵ 169 R³ R³¹ 394 R⁶ R⁴⁹ 619 R³² R⁶⁷ 844 R³⁶ R¹⁶ 170 R³ R³² 395 R⁶ R⁵⁰ 620 R³² R⁶⁸ 845 R³⁶ R¹⁷ 171 R³ R³³ 396 R⁶ R⁵¹ 621 R³² R⁶⁹ 846 R³⁶ R¹⁸ 172 R³ R³⁴ 397 R⁶ R⁵² 622 R³³ R¹  847 R³⁶ R¹⁹ 173 R³ R³⁵ 398 R⁶ R⁵³ 623 R³³ R²  848 R³⁶ R²⁰ 174 R³ R³⁶ 399 R⁶ R⁵⁴ 624 R³³ R³  849 R³⁶ R²¹ 175 R³ R³⁷ 400 R⁶ R⁵⁵ 625 R³³ R⁴  850 R³⁶ R²² 176 R³ R³⁸ 401 R⁶ R⁵⁶ 626 R³³ R⁵  851 R³⁶ R²³ 177 R³ R³⁹ 402 R⁶ R⁵⁷ 627 R³³ R⁶  852 R³⁶ R²⁴ 178 R³ R⁴⁰ 403 R⁶ R⁵⁸ 628 R³³ R⁷  853 R³⁶ R²⁵ 179 R³ R⁴¹ 404 R⁶ R⁵⁹ 629 R³³ R⁸  854 R³⁶ R²⁶ 180 R³ R⁴² 405 R⁶ R⁶⁰ 630 R³³ R⁹  855 R³⁶ R²⁷ 181 R³ R⁴³ 406 R⁶ R⁶¹ 631 R³³ R¹⁰ 856 R³⁶ R²⁸ 182 R³ R⁴⁴ 407 R⁶ R⁶² 632 R³³ R¹¹ 857 R³⁶ R²⁹ 183 R³ R⁴⁵ 408 R⁶ R⁶³ 633 R³³ R¹² 858 R³⁶ R³⁰ 184 R³ R⁴⁶ 409 R⁶ R⁶⁴ 634 R³³ R¹³ 859 R³⁶ R³¹ 185 R³ R⁴⁷ 410 R⁶ R⁶⁵ 635 R³³ R¹⁴ 860 R³⁶ R³² 186 R³ R⁴⁸ 411 R⁶ R⁶⁶ 636 R³³ R¹⁵ 861 R³⁶ R³³ 187 R³ R⁴⁹ 412 R⁶ R⁶⁷ 637 R³³ R¹⁶ 862 R³⁶ R³⁴ 188 R³ R⁵⁰ 413 R⁶ R⁶⁸ 638 R³³ R¹⁷ 863 R³⁶ R³⁵ 189 R³ R⁵¹ 414 R⁶ R⁶⁹ 639 R³³ R¹⁸ 864 R³⁶ R³⁶ 190 R³ R⁵² 415 R⁷ R¹  640 R³³ R¹⁹ 865 R³⁶ R³⁷ 191 R³ R⁵³ 416 R⁷ R²  641 R³³ R²⁰ 866 R³⁶ R³⁸ 192 R³ R⁵⁴ 417 R⁷ R³  642 R³³ R²¹ 867 R³⁶ R³⁹ 193 R³ R⁵⁵ 418 R⁷ R⁴  643 R³³ R²² 868 R³⁶ R⁴⁰ 194 R³ R⁵⁶ 419 R⁷ R⁵  644 R³³ R²³ 869 R³⁶ R⁴¹ 195 R³ R⁵⁷ 420 R⁷ R⁶  645 R³³ R²⁴ 870 R³⁶ R⁴² 196 R³ R⁵⁸ 421 R⁷ R⁷  646 R³³ R²⁵ 871 R³⁶ R⁴³ 197 R³ R⁵⁹ 422 R⁷ R⁸  647 R³³ R²⁶ 872 R³⁶ R⁴⁴ 198 R³ R⁶⁰ 423 R⁷ R⁹  648 R³³ R²⁷ 873 R³⁶ R⁴⁵ 199 R³ R⁶¹ 424 R⁷ R¹⁰ 649 R³³ R²⁸ 874 R³⁶ R⁴⁶ 200 R³ R⁶² 425 R⁷ R¹¹ 650 R³³ R²⁹ 875 R³⁶ R⁴⁷ 201 R³ R⁶³ 426 R⁷ R¹² 651 R³³ R³⁰ 876 R³⁶ R⁴⁸ 202 R³ R⁶⁴ 427 R⁷ R¹³ 652 R³³ R³¹ 877 R³⁶ R⁴⁹ 203 R³ R⁶⁵ 428 R⁷ R¹⁴ 653 R³³ R³² 878 R³⁶ R⁵⁰ 204 R³ R⁶⁶ 429 R⁷ R¹⁵ 654 R³³ R³³ 879 R³⁶ R⁵¹ 205 R³ R⁶⁷ 430 R⁷ R¹⁶ 655 R³³ R³⁴ 880 R³⁶ R⁵² 206 R³ R⁶⁸ 431 R⁷ R¹⁷ 656 R³³ R³⁵ 881 R³⁶ R⁵³ 207 R³ R⁶⁹ 432 R⁷ R¹⁸ 657 R³³ R³⁶ 882 R³⁶ R⁵⁴ 208 R⁴ R¹  433 R⁷ R¹⁹ 658 R³³ R³⁷ 883 R³⁶ R⁵⁵ 209 R⁴ R²  434 R⁷ R²⁰ 659 R³³ R³⁸ 884 R³⁶ R⁵⁶ 210 R⁴ R³  435 R⁷ R²¹ 660 R³³ R³⁹ 885 R³⁶ R⁵⁷ 211 R⁴ R⁴  436 R⁷ R²² 661 R³³ R⁴⁰ 886 R³⁶ R⁵⁸ 212 R⁴ R⁵  437 R⁷ R²³ 662 R³³ R⁴¹ 887 R³⁶ R⁵⁹ 213 R⁴ R⁶  438 R⁷ R²⁴ 663 R³³ R⁴² 888 R³⁶ R⁶⁰ 214 R⁴ R⁷  439 R⁷ R²⁵ 664 R³³ R⁴³ 889 R³⁶ R⁶¹ 215 R⁴ R⁸  440 R⁷ R²⁶ 665 R³³ R⁴⁴ 890 R³⁶ R⁶² 216 R⁴ R⁹  441 R⁷ R²⁷ 666 R³³ R⁴⁵ 891 R³⁶ R⁶³ 217 R⁴ R¹⁰ 442 R⁷ R²⁸ 667 R³³ R⁴⁶ 892 R³⁶ R⁶⁴ 218 R⁴ R¹¹ 443 R⁷ R²⁹ 668 R³³ R⁴⁷ 893 R³⁶ R⁶⁵ 219 R⁴ R¹² 444 R⁷ R³⁰ 669 R³³ R⁴⁸ 894 R³⁶ R⁶⁶ 220 R⁴ R¹³ 445 R⁷ R³¹ 670 R³³ R⁴⁹ 895 R³⁶ R⁶⁷ 221 R⁴ R¹⁴ 446 R⁷ R³² 671 R³³ R⁵⁰ 896 R³⁶ R⁶⁸ 222 R⁴ R¹⁵ 447 R⁷ R³³ 672 R³³ R⁵¹ 897 R³⁶ R⁶⁹ 223 R⁴ R¹⁶ 448 R⁷ R³⁴ 673 R³³ R⁵² 224 R⁴ R¹⁷ 449 R⁷ R³⁵ 674 R³³ R⁵³ 225 R⁴ R¹⁸ 450 R⁷ R³⁶ 675 R³³ R⁵⁴ wherein for each L_(Xi-n); L_(Xi-39) (i=1 to 1446) are based on Structure 39,

L_(Xi-40) (h=1 to 1446) is based on Structure 40,

L_(Xi-41) (h=1 to 1446) is based on Structure 41,

L_(Xi-42) (h=1 to 1446) is based on Structure 42,

L_(Xi-43) (h=1 to 1446) is based on Structure 43,

L_(Xi-44) (h=1 to 1446) is based on Structure 44,

L_(Xi-45) (h=1 to 1446) is based on Structure 45,

L_(Xi-46) (h=1 to 1446) is based on Structure 46,

L_(Xi-47) (h=1 to 1446) is based on Structure 47,

L_(Xi-48) (h=1 to 1446) is based on Structure 48,

L_(Xi-49) (h=1 to 1446) is based on Structure 49,

L_(Xi-50) (h=1 to 1446) is based on Structure 50,

L_(Xi-51) (h=1 to 1446) is based on Structure 51,

L_(Xi-52) (h=1 to 1446) is based on Structure 52,

L_(Xi-53) (h=1 to 1446) is based on Structure 53,

L_(Xi-54) (h=1 to 1446) is based on Structure 54,

L_(Xi-55) (h=1 to 1446) is based on Structure 55,

L_(Xi-56) (h=1 to 1446) is based on Structure 56,

L_(Xi-57) (i=1 to 1446) are based on, Structure 57,

where for each i, R^(E), R^(F), and R^(G) are defined as below:

i R^(E) R^(F) R^(G) i R^(E) R^(F) R^(G) i R^(E) R^(F) R^(G) 1 R¹ R¹  R¹  484 R² R¹  R¹  967 R³² R¹  R¹  2 R¹ R¹  R²  485 R² R¹  R²  968 R³² R¹  R²  3 R¹ R¹  R³  486 R² R¹  R³  969 R³² R¹  R³  4 R¹ R¹  R⁴  487 R² R¹  R⁴  970 R³² R¹  R⁴  5 R¹ R¹  R⁵  488 R² R¹  R⁵  971 R³² R¹  R⁵  6 R¹ R¹  R⁶  489 R² R¹  R⁶  972 R³² R¹  R⁶  7 R¹ R¹  R⁷  490 R² R¹  R⁷  973 R³² R¹  R⁷  8 R¹ R¹  R⁸  491 R² R¹  R⁸  974 R³² R¹  R⁸  9 R¹ R¹  R⁹  492 R² R¹  R⁹  975 R³² R¹  R⁹  10 R¹ R¹  R¹⁰ 493 R² R¹  R¹⁰ 976 R³² R¹  R¹⁰ 11 R¹ R¹  R¹¹ 494 R² R¹  R¹¹ 977 R³² R¹  R¹¹ 12 R¹ R¹  R¹² 495 R² R¹  R¹² 978 R³² R¹  R¹² 13 R¹ R¹  R¹³ 496 R² R¹  R¹³ 979 R³² R¹  R¹³ 14 R¹ R¹  R¹⁴ 497 R² R¹  R¹⁴ 980 R³² R¹  R¹⁴ 15 R¹ R¹  R¹⁵ 498 R² R¹  R¹⁵ 981 R³² R¹  R¹⁵ 16 R¹ R¹  R¹⁶ 499 R² R¹  R¹⁶ 982 R³² R¹  R¹⁶ 17 R¹ R¹  R¹⁷ 500 R² R¹  R¹⁷ 983 R³² R¹  R¹⁷ 18 R¹ R¹  R¹⁸ 501 R² R¹  R¹⁸ 984 R³² R¹  R¹⁸ 19 R¹ R¹  R¹⁹ 502 R² R¹  R¹⁹ 985 R³² R¹  R¹⁹ 20 R¹ R¹  R²⁰ 503 R² R¹  R²⁰ 986 R³² R¹  R²⁰ 21 R¹ R¹  R²¹ 504 R² R¹  R²¹ 987 R³² R¹  R²¹ 22 R¹ R¹  R²² 505 R² R¹  R²² 988 R³² R¹  R²² 23 R¹ R¹  R²³ 506 R² R¹  R²³ 989 R³² R¹  R²³ 24 R¹ R¹  R²⁴ 507 R² R¹  R²⁴ 990 R³² R¹  R²⁴ 25 R¹ R¹  R²⁵ 508 R² R¹  R²⁵ 991 R³² R¹  R²⁵ 26 R¹ R¹  R²⁶ 509 R² R¹  R²⁶ 992 R³² R¹  R²⁶ 27 R¹ R¹  R²⁷ 510 R² R¹  R²⁷ 993 R³² R¹  R²⁷ 28 R¹ R¹  R²⁸ 511 R² R¹  R²⁸ 994 R³² R¹  R²⁸ 29 R¹ R¹  R²⁹ 512 R² R¹  R²⁹ 995 R³² R¹  R²⁹ 30 R¹ R¹  R³⁰ 513 R² R¹  R³⁰ 996 R³² R¹  R³⁰ 31 R¹ R¹  R³¹ 514 R² R¹  R³¹ 997 R³² R¹  R³¹ 32 R¹ R¹  R³² 515 R² R¹  R³² 998 R³² R¹  R³² 33 R¹ R¹  R³³ 516 R² R¹  R³³ 999 R³² R¹  R³³ 34 R¹ R¹  R³⁴ 517 R² R¹  R³⁴ 1000 R³² R¹  R³⁴ 35 R¹ R¹  R³⁵ 518 R² R¹  R³⁵ 1001 R³² R¹  R³⁵ 36 R¹ R¹  R³⁶ 519 R² R¹  R³⁶ 1002 R³² R¹  R³⁶ 37 R¹ R¹  R³⁷ 520 R² R¹  R³⁷ 1003 R³² R¹  R³⁷ 38 R¹ R¹  R³⁸ 521 R² R¹  R³⁸ 1004 R³² R¹  R³⁸ 39 R¹ R¹  R³⁹ 522 R² R¹  R³⁹ 1005 R³² R¹  R³⁹ 40 R¹ R¹  R⁴⁰ 523 R² R¹  R⁴⁰ 1006 R³² R¹  R⁴⁰ 41 R¹ R¹  R⁴¹ 524 R² R¹  R⁴¹ 1007 R³² R¹  R⁴¹ 42 R¹ R¹  R⁴² 525 R² R¹  R⁴² 1008 R³² R¹  R⁴² 43 R¹ R¹  R⁴³ 526 R² R¹  R⁴³ 1009 R³² R¹  R⁴³ 44 R¹ R¹  R⁴⁴ 527 R² R¹  R⁴⁴ 1010 R³² R¹  R⁴⁴ 45 R¹ R¹  R⁴⁵ 528 R² R¹  R⁴⁵ 1011 R³² R¹  R⁴⁵ 46 R¹ R¹  R⁴⁶ 529 R² R¹  R⁴⁶ 1012 R³² R¹  R⁴⁶ 47 R¹ R¹  R⁴⁷ 530 R² R¹  R⁴⁷ 1013 R³² R¹  R⁴⁷ 48 R¹ R¹  R⁴⁸ 531 R² R¹  R⁴⁸ 1014 R³² R¹  R⁴⁸ 49 R¹ R¹  R⁴⁹ 532 R² R¹  R⁴⁹ 1015 R³² R¹  R⁴⁹ 50 R¹ R¹  R⁵⁰ 533 R² R¹  R⁵⁰ 1016 R³² R¹  R⁵⁰ 51 R¹ R¹  R⁵¹ 534 R² R¹  R⁵¹ 1017 R³² R¹  R⁵¹ 52 R¹ R¹  R⁵² 535 R² R¹  R⁵² 1018 R³² R¹  R⁵² 53 R¹ R¹  R⁵³ 536 R² R¹  R⁵³ 1019 R³² R¹  R⁵³ 54 R¹ R¹  R⁵⁴ 537 R² R¹  R⁵⁴ 1020 R³² R¹  R⁵⁴ 55 R¹ R¹  R⁵⁵ 538 R² R¹  R⁵⁵ 1021 R³² R¹  R⁵⁵ 56 R¹ R¹  R⁵⁶ 539 R² R¹  R⁵⁶ 1022 R³² R¹  R⁵⁶ 57 R¹ R¹  R⁵⁷ 540 R² R¹  R⁵⁷ 1023 R³² R¹  R⁵⁷ 58 R¹ R¹  R⁵⁸ 541 R² R¹  R⁵⁸ 1024 R³² R¹  R⁵⁸ 59 R¹ R¹  R⁵⁹ 542 R² R¹  R⁵⁹ 1025 R³² R¹  R⁵⁹ 60 R¹ R¹  R⁶⁰ 543 R² R¹  R⁶⁰ 1026 R³² R¹  R⁶⁰ 61 R¹ R¹  R⁶¹ 544 R² R¹  R⁶¹ 1027 R³² R¹  R⁶¹ 62 R¹ R¹  R⁶² 545 R² R¹  R⁶² 1028 R³² R¹  R⁶² 63 R¹ R¹  R⁶³ 546 R² R¹  R⁶³ 1029 R³² R¹  R⁶³ 64 R¹ R¹  R⁶⁴ 547 R² R¹  R⁶⁴ 1030 R³² R¹  R⁶⁴ 65 R¹ R¹  R⁶⁵ 548 R² R¹  R⁶⁵ 1031 R³² R¹  R⁶⁵ 66 R¹ R¹  R⁶⁶ 549 R² R¹  R⁶⁶ 1032 R³² R¹  R⁶⁶ 67 R¹ R¹  R⁶⁷ 550 R² R¹  R⁶⁷ 1033 R³² R¹  R⁶⁷ 68 R¹ R¹  R⁶⁸ 551 R² R¹  R⁶⁸ 1034 R³² R¹  R⁶⁸ 69 R¹ R¹  R⁶⁹ 552 R² R¹  R⁶⁹ 1035 R³² R¹  R⁶⁹ 70 R¹ R²  R¹  553 R² R²  R¹  1036 R³² R²  R¹  71 R¹ R²  R²  554 R² R²  R²  1037 R³² R²  R²  72 R¹ R²  R³  555 R² R²  R³  1038 R³² R²  R³  73 R¹ R²  R⁴  556 R² R²  R⁴  1039 R³² R²  R⁴  74 R¹ R²  R⁵  557 R² R²  R⁵  1040 R³² R²  R⁵  75 R¹ R²  R⁶  558 R² R²  R⁶  1041 R³² R²  R⁶  76 R¹ R²  R⁷  559 R² R²  R⁷  1042 R³² R²  R⁷  77 R¹ R²  R⁸  560 R² R²  R⁸  1043 R³² R²  R⁸  78 R¹ R²  R⁹  561 R² R²  R⁹  1044 R³² R²  R⁹  79 R¹ R²  R¹⁰ 562 R² R²  R¹⁰ 1045 R³² R²  R¹⁰ 80 R¹ R²  R¹¹ 563 R² R²  R¹¹ 1046 R³² R²  R¹¹ 81 R¹ R²  R¹² 564 R² R²  R¹² 1047 R³² R²  R¹² 82 R¹ R²  R¹³ 565 R² R²  R¹³ 1048 R³² R²  R¹³ 83 R¹ R²  R¹⁴ 566 R² R²  R¹⁴ 1049 R³² R²  R¹⁴ 84 R¹ R²  R¹⁵ 567 R² R²  R¹⁵ 1050 R³² R²  R¹⁵ 85 R¹ R²  R¹⁶ 568 R² R²  R¹⁶ 1051 R³² R²  R¹⁶ 86 R¹ R²  R¹⁷ 569 R² R²  R¹⁷ 1052 R³² R²  R¹⁷ 87 R¹ R²  R¹⁸ 570 R² R²  R¹⁸ 1053 R³² R²  R¹⁸ 88 R¹ R²  R¹⁹ 571 R² R²  R¹⁹ 1054 R³² R²  R¹⁹ 89 R¹ R²  R²⁰ 572 R² R²  R²⁰ 1055 R³² R²  R²⁰ 90 R¹ R²  R²¹ 573 R² R²  R²¹ 1056 R³² R²  R²¹ 91 R¹ R²  R²² 574 R² R²  R²² 1057 R³² R²  R²² 92 R¹ R²  R²³ 575 R² R²  R²³ 1058 R³² R²  R²³ 93 R¹ R²  R²⁴ 576 R² R²  R²⁴ 1059 R³² R²  R²⁴ 94 R¹ R²  R²⁵ 577 R² R²  R²⁵ 1060 R³² R²  R²⁵ 95 R¹ R²  R²⁶ 578 R² R²  R²⁶ 1061 R³² R²  R²⁶ 96 R¹ R²  R²⁷ 579 R² R²  R²⁷ 1062 R³² R²  R²⁷ 97 R¹ R²  R²⁸ 580 R² R²  R²⁸ 1063 R³² R²  R²⁸ 98 R¹ R²  R²⁹ 581 R² R²  R²⁹ 1064 R³² R²  R²⁹ 99 R¹ R²  R³⁰ 582 R² R²  R³⁰ 1065 R³² R²  R³⁰ 100 R¹ R²  R³¹ 583 R² R²  R³¹ 1066 R³² R²  R³¹ 101 R¹ R²  R³² 584 R² R²  R³² 1067 R³² R²  R³² 102 R¹ R²  R³³ 585 R² R²  R³³ 1068 R³² R²  R³³ 103 R¹ R²  R³⁴ 586 R² R²  R³⁴ 1069 R³² R²  R³⁴ 104 R¹ R²  R³⁵ 587 R² R²  R³⁵ 1070 R³² R²  R³⁵ 105 R¹ R²  R³⁶ 588 R² R²  R³⁶ 1071 R³² R²  R³⁶ 106 R¹ R²  R³⁷ 589 R² R²  R³⁷ 1072 R³² R²  R³⁷ 107 R¹ R²  R³⁸ 590 R² R²  R³⁸ 1073 R³² R²  R³⁸ 108 R¹ R²  R³⁹ 591 R² R²  R³⁹ 1074 R³² R²  R³⁹ 109 R¹ R²  R⁴⁰ 592 R² R²  R⁴⁰ 1075 R³² R²  R⁴⁰ 110 R¹ R²  R⁴¹ 593 R² R²  R⁴¹ 1076 R³² R²  R⁴¹ 111 R¹ R²  R⁴² 594 R² R²  R⁴² 1077 R³² R²  R⁴² 112 R¹ R²  R⁴³ 595 R² R²  R⁴³ 1078 R³² R²  R⁴³ 113 R¹ R²  R⁴⁴ 596 R² R²  R⁴⁴ 1079 R³² R²  R⁴⁴ 114 R¹ R²  R⁴⁵ 597 R² R²  R⁴⁵ 1080 R³² R²  R⁴⁵ 115 R¹ R²  R⁴⁶ 598 R² R²  R⁴⁶ 1081 R³² R²  R⁴⁶ 116 R¹ R²  R⁴⁷ 599 R² R²  R⁴⁷ 1082 R³² R²  R⁴⁷ 117 R¹ R²  R⁴⁸ 600 R² R²  R⁴⁸ 1083 R³² R²  R⁴⁸ 118 R¹ R²  R⁴⁹ 601 R² R²  R⁴⁹ 1084 R³² R²  R⁴⁹ 119 R¹ R²  R⁵⁰ 602 R² R²  R⁵⁰ 1085 R³² R²  R⁵⁰ 120 R¹ R²  R⁵¹ 603 R² R²  R⁵¹ 1086 R³² R²  R⁵¹ 121 R¹ R²  R⁵² 604 R² R²  R⁵² 1087 R³² R²  R⁵² 122 R¹ R²  R⁵³ 605 R² R²  R⁵³ 1088 R³² R²  R⁵³ 123 R¹ R²  R⁵⁴ 606 R² R²  R⁵⁴ 1089 R³² R²  R⁵⁴ 124 R¹ R²  R⁵⁵ 607 R² R²  R⁵⁵ 1090 R³² R²  R⁵⁵ 125 R¹ R²  R⁵⁶ 608 R² R²  R⁵⁶ 1091 R³² R²  R⁵⁶ 126 R¹ R²  R⁵⁷ 609 R² R²  R⁵⁷ 1092 R³² R²  R⁵⁷ 127 R¹ R²  R⁵⁸ 610 R² R²  R⁵⁸ 1093 R³² R²  R⁵⁸ 128 R¹ R²  R⁵⁹ 611 R² R²  R⁵⁹ 1094 R³² R²  R⁵⁹ 129 R¹ R²  R⁶⁰ 612 R² R²  R⁶⁰ 1095 R³² R²  R⁶⁰ 130 R¹ R²  R⁶¹ 613 R² R²  R⁶¹ 1096 R³² R²  R⁶¹ 131 R¹ R²  R⁶² 614 R² R²  R⁶² 1097 R³² R²  R⁶² 132 R¹ R²  R⁶³ 615 R² R²  R⁶³ 1098 R³² R²  R⁶³ 133 R¹ R²  R⁶⁴ 616 R² R²  R⁶⁴ 1099 R³² R²  R⁶⁴ 134 R¹ R²  R⁶⁵ 617 R² R²  R⁶⁵ 1100 R³² R²  R⁶⁵ 135 R¹ R²  R⁶⁶ 618 R² R²  R⁶⁶ 1101 R³² R²  R⁶⁶ 136 R¹ R²  R⁶⁷ 619 R² R²  R⁶⁷ 1102 R³² R²  R⁶⁷ 137 R¹ R²  R⁶⁸ 620 R² R²  R⁶⁸ 1103 R³² R²  R⁶⁸ 138 R¹ R²  R⁶⁹ 621 R² R²  R⁶⁹ 1104 R³² R²  R⁶⁹ 139 R¹ R⁷  R¹  622 R² R⁷  R¹  1105 R³² R⁷  R¹  140 R¹ R⁷  R²  623 R² R⁷  R²  1106 R³² R⁷  R²  141 R¹ R⁷  R³  624 R² R⁷  R³  1107 R³² R⁷  R³  142 R¹ R⁷  R⁴  625 R² R⁷  R⁴  1108 R³² R⁷  R⁴  143 R¹ R⁷  R⁵  626 R² R⁷  R⁵  1109 R³² R⁷  R⁵  144 R¹ R⁷  R⁶  627 R² R⁷  R⁶  1110 R³² R⁷  R⁶  145 R¹ R⁷  R⁷  628 R² R⁷  R⁷  1111 R³² R⁷  R⁷  146 R¹ R⁷  R⁸  629 R² R⁷  R⁸  1112 R³² R⁷  R⁸  147 R¹ R⁷  R⁹  630 R² R⁷  R⁹  1113 R³² R⁷  R⁹  148 R¹ R⁷  R¹⁰ 631 R² R⁷  R¹⁰ 1114 R³² R⁷  R¹⁰ 149 R¹ R⁷  R¹¹ 632 R² R⁷  R¹¹ 1115 R³² R⁷  R¹¹ 150 R¹ R⁷  R¹² 633 R² R⁷  R¹² 1116 R³² R⁷  R¹² 151 R¹ R⁷  R¹³ 634 R² R⁷  R¹³ 1117 R³² R⁷  R¹³ 152 R¹ R⁷  R¹⁴ 635 R² R⁷  R¹⁴ 1118 R³² R⁷  R¹⁴ 153 R¹ R⁷  R¹⁵ 636 R² R⁷  R¹⁵ 1119 R³² R⁷  R¹⁵ 154 R¹ R⁷  R¹⁶ 637 R² R⁷  R¹⁶ 1120 R³² R⁷  R¹⁶ 155 R¹ R⁷  R¹⁷ 638 R² R⁷  R¹⁷ 1121 R³² R⁷  R¹⁷ 156 R¹ R⁷  R¹⁸ 639 R² R⁷  R¹⁸ 1122 R³² R⁷  R¹⁸ 157 R¹ R⁷  R¹⁹ 640 R² R⁷  R¹⁹ 1123 R³² R⁷  R¹⁹ 158 R¹ R⁷  R²⁰ 641 R² R⁷  R²⁰ 1124 R³² R⁷  R²⁰ 159 R¹ R⁷  R²¹ 642 R² R⁷  R²¹ 1125 R³² R⁷  R²¹ 160 R¹ R⁷  R²² 643 R² R⁷  R²² 1126 R³² R⁷  R²² 161 R¹ R⁷  R²³ 644 R² R⁷  R²³ 1127 R³² R⁷  R²³ 162 R¹ R⁷  R²⁴ 645 R² R⁷  R²⁴ 1128 R³² R⁷  R²⁴ 163 R¹ R⁷  R²⁵ 646 R² R⁷  R²⁵ 1129 R³² R⁷  R²⁵ 164 R¹ R⁷  R²⁶ 647 R² R⁷  R²⁶ 1130 R³² R⁷  R²⁶ 165 R¹ R⁷  R²⁷ 648 R² R⁷  R²⁷ 1131 R³² R⁷  R²⁷ 166 R¹ R⁷  R²⁸ 649 R² R⁷  R²⁸ 1132 R³² R⁷  R²⁸ 167 R¹ R⁷  R²⁹ 650 R² R⁷  R²⁹ 1133 R³² R⁷  R²⁹ 168 R¹ R⁷  R³⁰ 651 R² R⁷  R³⁰ 1134 R³² R⁷  R³⁰ 169 R¹ R⁷  R³¹ 652 R² R⁷  R³¹ 1135 R³² R⁷  R³¹ 170 R¹ R⁷  R³² 653 R² R⁷  R³² 1136 R³² R⁷  R³² 171 R¹ R⁷  R³³ 654 R² R⁷  R³³ 1137 R³² R⁷  R³³ 172 R¹ R⁷  R³⁴ 655 R² R⁷  R³⁴ 1138 R³² R⁷  R³⁴ 173 R¹ R⁷  R³⁵ 656 R² R⁷  R³⁵ 1139 R³² R⁷  R³⁵ 174 R¹ R⁷  R³⁶ 657 R² R⁷  R³⁶ 1140 R³² R⁷  R³⁶ 175 R¹ R⁷  R³⁷ 658 R² R⁷  R³⁷ 1141 R³² R⁷  R³⁷ 176 R¹ R⁷  R³⁸ 659 R² R⁷  R³⁸ 1142 R³² R⁷  R³⁸ 177 R¹ R⁷  R³⁹ 660 R² R⁷  R³⁹ 1143 R³² R⁷  R³⁹ 178 R¹ R⁷  R⁴⁰ 661 R² R⁷  R⁴⁰ 1144 R³² R⁷  R⁴⁰ 179 R¹ R⁷  R⁴¹ 662 R² R⁷  R⁴¹ 1145 R³² R⁷  R⁴¹ 180 R¹ R⁷  R⁴² 663 R² R⁷  R⁴² 1146 R³² R⁷  R⁴² 181 R¹ R⁷  R⁴³ 664 R² R⁷  R⁴³ 1147 R³² R⁷  R⁴³ 182 R¹ R⁷  R⁴⁴ 665 R² R⁷  R⁴⁴ 1148 R³² R⁷  R⁴⁴ 183 R¹ R⁷  R⁴⁵ 666 R² R⁷  R⁴⁵ 1149 R³² R⁷  R⁴⁵ 184 R¹ R⁷  R⁴⁶ 667 R² R⁷  R⁴⁶ 1150 R³² R⁷  R⁴⁶ 185 R¹ R⁷  R⁴⁷ 668 R² R⁷  R⁴⁷ 1151 R³² R⁷  R⁴⁷ 186 R¹ R⁷  R⁴⁸ 669 R² R⁷  R⁴⁸ 1152 R³² R⁷  R⁴⁸ 187 R¹ R⁷  R⁴⁹ 670 R² R⁷  R⁴⁹ 1153 R³² R⁷  R⁴⁹ 188 R¹ R⁷  R⁵⁰ 671 R² R⁷  R⁵⁰ 1154 R³² R⁷  R⁵⁰ 189 R¹ R⁷  R⁵¹ 672 R² R⁷  R⁵¹ 1155 R³² R⁷  R⁵¹ 190 R¹ R⁷  R⁵² 673 R² R⁷  R⁵² 1156 R³² R⁷  R⁵² 191 R¹ R⁷  R⁵³ 674 R² R⁷  R⁵³ 1157 R³² R⁷  R⁵³ 192 R¹ R⁷  R⁵⁴ 675 R² R⁷  R⁵⁴ 1158 R³² R⁷  R⁵⁴ 193 R¹ R⁷  R⁵⁵ 676 R² R⁷  R⁵⁵ 1159 R³² R⁷  R⁵⁵ 194 R¹ R⁷  R⁵⁶ 677 R² R⁷  R⁵⁶ 1160 R³² R⁷  R⁵⁶ 195 R¹ R⁷  R⁵⁷ 678 R² R⁷  R⁵⁷ 1161 R³² R⁷  R⁵⁷ 196 R¹ R⁷  R⁵⁸ 679 R² R⁷  R⁵⁸ 1162 R³² R⁷  R⁵⁸ 197 R¹ R⁷  R⁵⁹ 680 R² R⁷  R⁵⁹ 1163 R³² R⁷  R⁵⁹ 198 R¹ R⁷  R⁶⁰ 681 R² R⁷  R⁶⁰ 1164 R³² R⁷  R⁶⁰ 199 R¹ R⁷  R⁶¹ 682 R² R⁷  R⁶¹ 1165 R³² R⁷  R⁶¹ 200 R¹ R⁷  R⁶² 683 R² R⁷  R⁶² 1166 R³² R⁷  R⁶² 201 R¹ R⁷  R⁶³ 684 R² R⁷  R⁶³ 1167 R³² R⁷  R⁶³ 202 R¹ R⁷  R⁶⁴ 685 R² R⁷  R⁶⁴ 1168 R³² R⁷  R⁶⁴ 203 R¹ R⁷  R⁶⁵ 686 R² R⁷  R⁶⁵ 1169 R³² R⁷  R⁶⁵ 204 R¹ R⁷  R⁶⁶ 687 R² R⁷  R⁶⁶ 1170 R³² R⁷  R⁶⁶ 205 R¹ R⁷  R⁶⁷ 688 R² R⁷  R⁶⁷ 1171 R³² R⁷  R⁶⁷ 206 R¹ R⁷  R⁶⁸ 689 R² R⁷  R⁶⁸ 1172 R³² R⁷  R⁶⁸ 207 R¹ R⁷  R⁶⁹ 690 R² R⁷  R⁶⁹ 1173 R³² R⁷  R⁶⁹ 208 R¹ R¹⁴ R¹  691 R² R¹⁴ R¹  1174 R³² R¹⁴ R¹  209 R¹ R¹⁴ R²  692 R² R¹⁴ R²  1175 R³² R¹⁴ R²  210 R¹ R¹⁴ R³  693 R² R¹⁴ R³  1176 R³² R¹⁴ R³  211 R¹ R¹⁴ R⁴  694 R² R¹⁴ R⁴  1177 R³² R¹⁴ R⁴  212 R¹ R¹⁴ R⁵  695 R² R¹⁴ R⁵  1178 R³² R¹⁴ R⁵  213 R¹ R¹⁴ R⁶  696 R² R¹⁴ R⁶  1179 R³² R¹⁴ R⁶  214 R¹ R¹⁴ R⁷  697 R² R¹⁴ R⁷  1180 R³² R¹⁴ R⁷  215 R¹ R¹⁴ R⁸  698 R² R¹⁴ R⁸  1181 R³² R¹⁴ R⁸  216 R¹ R¹⁴ R⁹  699 R² R¹⁴ R⁹  1182 R³² R¹⁴ R⁹  217 R¹ R¹⁴ R¹⁰ 700 R² R¹⁴ R¹⁰ 1183 R³² R¹⁴ R¹⁰ 218 R¹ R¹⁴ R¹¹ 701 R² R¹⁴ R¹¹ 1184 R³² R¹⁴ R¹¹ 219 R¹ R¹⁴ R¹² 702 R² R¹⁴ R¹² 1185 R³² R¹⁴ R¹² 220 R¹ R¹⁴ R¹³ 703 R² R¹⁴ R¹³ 1186 R³² R¹⁴ R¹³ 221 R¹ R¹⁴ R¹⁴ 704 R² R¹⁴ R¹⁴ 1187 R³² R¹⁴ R¹⁴ 222 R¹ R¹⁴ R¹⁵ 705 R² R¹⁴ R¹⁵ 1188 R³² R¹⁴ R¹⁵ 223 R¹ R¹⁴ R¹⁶ 706 R² R¹⁴ R¹⁶ 1189 R³² R¹⁴ R¹⁶ 224 R¹ R¹⁴ R¹⁷ 707 R² R¹⁴ R¹⁷ 1190 R³² R¹⁴ R¹⁷ 225 R¹ R¹⁴ R¹⁸ 708 R² R¹⁴ R¹⁸ 1191 R³² R¹⁴ R¹⁸ 226 R¹ R¹⁴ R¹⁹ 709 R² R¹⁴ R¹⁹ 1192 R³² R¹⁴ R¹⁹ 227 R¹ R¹⁴ R²⁰ 710 R² R¹⁴ R²⁰ 1193 R³² R¹⁴ R²⁰ 228 R¹ R¹⁴ R²¹ 711 R² R¹⁴ R²¹ 1194 R³² R¹⁴ R²¹ 229 R¹ R¹⁴ R²² 712 R² R¹⁴ R²² 1195 R³² R¹⁴ R²² 230 R¹ R¹⁴ R²³ 713 R² R¹⁴ R²³ 1196 R³² R¹⁴ R²³ 231 R¹ R¹⁴ R²⁴ 714 R² R¹⁴ R²⁴ 1197 R³² R¹⁴ R²⁴ 232 R¹ R¹⁴ R²⁵ 715 R² R¹⁴ R²⁵ 1198 R³² R¹⁴ R²⁵ 233 R¹ R¹⁴ R²⁶ 716 R² R¹⁴ R²⁶ 1199 R³² R¹⁴ R²⁶ 234 R¹ R¹⁴ R²⁷ 717 R² R¹⁴ R²⁷ 1200 R³² R¹⁴ R²⁷ 235 R¹ R¹⁴ R²⁸ 718 R² R¹⁴ R²⁸ 1201 R³² R¹⁴ R²⁸ 236 R¹ R¹⁴ R²⁹ 719 R² R¹⁴ R²⁹ 1202 R³² R¹⁴ R²⁹ 237 R¹ R¹⁴ R³⁰ 720 R² R¹⁴ R³⁰ 1203 R³² R¹⁴ R³⁰ 238 R¹ R¹⁴ R³¹ 721 R² R¹⁴ R³¹ 1204 R³² R¹⁴ R³¹ 239 R¹ R¹⁴ R³² 722 R² R¹⁴ R³² 1205 R³² R¹⁴ R³² 240 R¹ R¹⁴ R³³ 723 R² R¹⁴ R³³ 1206 R³² R¹⁴ R³³ 241 R¹ R¹⁴ R³⁴ 724 R² R¹⁴ R³⁴ 1207 R³² R¹⁴ R³⁴ 242 R¹ R¹⁴ R³⁵ 725 R² R¹⁴ R³⁵ 1208 R³² R¹⁴ R³⁵ 243 R¹ R¹⁴ R³⁶ 726 R² R¹⁴ R³⁶ 1209 R³² R¹⁴ R³⁶ 244 R¹ R¹⁴ R³⁷ 727 R² R¹⁴ R³⁷ 1210 R³² R¹⁴ R³⁷ 245 R¹ R¹⁴ R³⁸ 728 R² R¹⁴ R³⁸ 1211 R³² R¹⁴ R³⁸ 246 R¹ R¹⁴ R³⁹ 729 R² R¹⁴ R³⁹ 1212 R³² R¹⁴ R³⁹ 247 R¹ R¹⁴ R⁴⁰ 730 R² R¹⁴ R⁴⁰ 1213 R³² R¹⁴ R⁴⁰ 248 R¹ R¹⁴ R⁴¹ 731 R² R¹⁴ R⁴¹ 1214 R³² R¹⁴ R⁴¹ 249 R¹ R¹⁴ R⁴² 732 R² R¹⁴ R⁴² 1215 R³² R¹⁴ R⁴² 250 R¹ R¹⁴ R⁴³ 733 R² R¹⁴ R⁴³ 1216 R³² R¹⁴ R⁴³ 251 R¹ R¹⁴ R⁴⁴ 734 R² R¹⁴ R⁴⁴ 1217 R³² R¹⁴ R⁴⁴ 252 R¹ R¹⁴ R⁴⁵ 735 R² R¹⁴ R⁴⁵ 1218 R³² R¹⁴ R⁴⁵ 253 R¹ R¹⁴ R⁴⁶ 736 R² R¹⁴ R⁴⁶ 1219 R³² R¹⁴ R⁴⁶ 254 R¹ R¹⁴ R⁴⁷ 737 R² R¹⁴ R⁴⁷ 1220 R³² R¹⁴ R⁴⁷ 255 R¹ R¹⁴ R⁴⁸ 738 R² R¹⁴ R⁴⁸ 1221 R³² R¹⁴ R⁴⁸ 256 R¹ R¹⁴ R⁴⁹ 739 R² R¹⁴ R⁴⁹ 1222 R³² R¹⁴ R⁴⁹ 257 R¹ R¹⁴ R⁵⁰ 740 R² R¹⁴ R⁵⁰ 1223 R³² R¹⁴ R⁵⁰ 258 R¹ R¹⁴ R⁵¹ 741 R² R¹⁴ R⁵¹ 1224 R³² R¹⁴ R⁵¹ 259 R¹ R¹⁴ R⁵² 742 R² R¹⁴ R⁵² 1225 R³² R¹⁴ R⁵² 260 R¹ R¹⁴ R⁵³ 743 R² R¹⁴ R⁵³ 1226 R³² R¹⁴ R⁵³ 261 R¹ R¹⁴ R⁵⁴ 744 R² R¹⁴ R⁵⁴ 1227 R³² R¹⁴ R⁵⁴ 262 R¹ R¹⁴ R⁵⁵ 745 R² R¹⁴ R⁵⁵ 1228 R³² R¹⁴ R⁵⁵ 263 R¹ R¹⁴ R⁵⁶ 746 R² R¹⁴ R⁵⁶ 1229 R³² R¹⁴ R⁵⁶ 264 R¹ R¹⁴ R⁵⁷ 747 R² R¹⁴ R⁵⁷ 1230 R³² R¹⁴ R⁵⁷ 265 R¹ R¹⁴ R⁵⁸ 748 R² R¹⁴ R⁵⁸ 1231 R³² R¹⁴ R⁵⁸ 266 R¹ R¹⁴ R⁵⁹ 749 R² R¹⁴ R⁵⁹ 1232 R³² R¹⁴ R⁵⁹ 267 R¹ R¹⁴ R⁶⁰ 750 R² R¹⁴ R⁶⁰ 1233 R³² R¹⁴ R⁶⁰ 268 R¹ R¹⁴ R⁶¹ 751 R² R¹⁴ R⁶¹ 1234 R³² R¹⁴ R⁶¹ 269 R¹ R¹⁴ R⁶² 752 R² R¹⁴ R⁶² 1235 R³² R¹⁴ R⁶² 270 R¹ R¹⁴ R⁶³ 753 R² R¹⁴ R⁶³ 1236 R³² R¹⁴ R⁶³ 271 R¹ R¹⁴ R⁶⁴ 754 R² R¹⁴ R⁶⁴ 1237 R³² R¹⁴ R⁶⁴ 272 R¹ R¹⁴ R⁶⁵ 755 R² R¹⁴ R⁶⁵ 1238 R³² R¹⁴ R⁶⁵ 273 R¹ R¹⁴ R⁶⁶ 756 R² R¹⁴ R⁶⁶ 1239 R³² R¹⁴ R⁶⁶ 274 R¹ R¹⁴ R⁶⁷ 757 R² R¹⁴ R⁶⁷ 1240 R³² R¹⁴ R⁶⁷ 275 R¹ R¹⁴ R⁶⁸ 758 R² R¹⁴ R⁶⁸ 1241 R³² R¹⁴ R⁶⁸ 276 R¹ R¹⁴ R⁶⁹ 759 R² R¹⁴ R⁶⁹ 1242 R³² R¹⁴ R⁶⁹ 277 R¹ R³² R¹  760 R² R³² R¹  1243 R³² R³² R¹  278 R¹ R³² R²  761 R² R³² R²  1244 R³² R³² R²  279 R¹ R³² R³  762 R² R³² R³  1245 R³² R³² R³  280 R¹ R³² R⁴  763 R² R³² R⁴  1246 R³² R³² R⁴  281 R¹ R³² R⁵  764 R² R³² R⁵  1247 R³² R³² R⁵  282 R¹ R³² R⁶  765 R² R³² R⁶  1248 R³² R³² R⁶  283 R¹ R³² R⁷  766 R² R³² R⁷  1249 R³² R³² R⁷  284 R¹ R³² R⁸  767 R² R³² R⁸  1250 R³² R³² R⁸  285 R¹ R³² R⁹  768 R² R³² R⁹  1251 R³² R³² R⁹  286 R¹ R³² R¹⁰ 769 R² R³² R¹⁰ 1252 R³² R³² R¹⁰ 287 R¹ R³² R¹¹ 770 R² R³² R¹¹ 1253 R³² R³² R¹¹ 288 R¹ R³² R¹² 771 R² R³² R¹² 1254 R³² R³² R¹² 289 R¹ R³² R¹³ 772 R² R³² R¹³ 1255 R³² R³² R¹³ 290 R¹ R³² R¹⁴ 773 R² R³² R¹⁴ 1256 R³² R³² R¹⁴ 291 R¹ R³² R¹⁵ 774 R² R³² R¹⁵ 1257 R³² R³² R¹⁵ 292 R¹ R³² R¹⁶ 775 R² R³² R¹⁶ 1258 R³² R³² R¹⁶ 293 R¹ R³² R¹⁷ 776 R² R³² R¹⁷ 1259 R³² R³² R¹⁷ 294 R¹ R³² R¹⁸ 777 R² R³² R¹⁸ 1260 R³² R³² R¹⁸ 295 R¹ R³² R¹⁹ 778 R² R³² R¹⁹ 1261 R³² R³² R¹⁹ 296 R¹ R³² R²⁰ 779 R² R³² R²⁰ 1262 R³² R³² R²⁰ 297 R¹ R³² R²¹ 780 R² R³² R²¹ 1263 R³² R³² R²¹ 298 R¹ R³² R²² 781 R² R³² R²² 1264 R³² R³² R²² 299 R¹ R³² R²³ 782 R² R³² R²³ 1265 R³² R³² R²³ 300 R¹ R³² R²⁴ 783 R² R³² R²⁴ 1266 R³² R³² R²⁴ 301 R¹ R³² R²⁵ 784 R² R³² R²⁵ 1267 R³² R³² R²⁵ 302 R¹ R³² R²⁶ 785 R² R³² R²⁶ 1268 R³² R³² R²⁶ 303 R¹ R³² R²⁷ 786 R² R³² R²⁷ 1269 R³² R³² R²⁷ 304 R¹ R³² R²⁸ 787 R² R³² R²⁸ 1270 R³² R³² R²⁸ 305 R¹ R³² R²⁹ 788 R² R³² R²⁹ 1271 R³² R³² R²⁹ 306 R¹ R³² R³⁰ 789 R² R³² R³⁰ 1272 R³² R³² R³⁰ 307 R¹ R³² R³¹ 790 R² R³² R³¹ 1273 R³² R³² R³¹ 308 R¹ R³² R³² 791 R² R³² R³² 1274 R³² R³² R³² 309 R¹ R³² R³³ 792 R² R³² R³³ 1275 R³² R³² R³³ 310 R¹ R³² R³⁴ 793 R² R³² R³⁴ 1276 R³² R³² R³⁴ 311 R¹ R³² R³⁵ 794 R² R³² R³⁵ 1277 R³² R³² R³⁵ 312 R¹ R³² R³⁶ 795 R² R³² R³⁶ 1278 R³² R³² R³⁶ 313 R¹ R³² R³⁷ 796 R² R³² R³⁷ 1279 R³² R³² R³⁷ 314 R¹ R³² R³⁸ 797 R² R³² R³⁸ 1280 R³² R³² R³⁸ 315 R¹ R³² R³⁹ 798 R² R³² R³⁹ 1281 R³² R³² R³⁹ 316 R¹ R³² R⁴⁰ 799 R² R³² R⁴⁰ 1282 R³² R³² R⁴⁰ 317 R¹ R³² R⁴¹ 800 R² R³² R⁴¹ 1283 R³² R³² R⁴¹ 318 R¹ R³² R⁴² 801 R² R³² R⁴² 1284 R³² R³² R⁴² 319 R¹ R³² R⁴³ 802 R² R³² R⁴³ 1285 R³² R³² R⁴³ 320 R¹ R³² R⁴⁴ 803 R² R³² R⁴⁴ 1286 R³² R³² R⁴⁴ 321 R¹ R³² R⁴⁵ 804 R² R³² R⁴⁵ 1287 R³² R³² R⁴⁵ 322 R¹ R³² R⁴⁶ 805 R² R³² R⁴⁶ 1288 R³² R³² R⁴⁶ 323 R¹ R³² R⁴⁷ 806 R² R³² R⁴⁷ 1289 R³² R³² R⁴⁷ 324 R¹ R³² R⁴⁸ 807 R² R³² R⁴⁸ 1290 R³² R³² R⁴⁸ 325 R¹ R³² R⁴⁹ 808 R² R³² R⁴⁹ 1291 R³² R³² R⁴⁹ 326 R¹ R³² R⁵⁰ 809 R² R³² R⁵⁰ 1292 R³² R³² R⁵⁰ 327 R¹ R³² R⁵¹ 810 R² R³² R⁵¹ 1293 R³² R³² R⁵¹ 328 R¹ R³² R⁵² 811 R² R³² R⁵² 1294 R³² R³² R⁵² 329 R¹ R³² R⁵³ 812 R² R³² R⁵³ 1295 R³² R³² R⁵³ 330 R¹ R³² R⁵⁴ 813 R² R³² R⁵⁴ 1296 R³² R³² R⁵⁴ 331 R¹ R³² R⁵⁵ 814 R² R³² R⁵⁵ 1297 R³² R³² R⁵⁵ 332 R¹ R³² R⁵⁶ 815 R² R³² R⁵⁶ 1298 R³² R³² R⁵⁶ 333 R¹ R³² R⁵⁷ 816 R² R³² R⁵⁷ 1299 R³² R³² R⁵⁷ 334 R¹ R³² R⁵⁸ 817 R² R³² R⁵⁸ 1300 R³² R³² R⁵⁸ 335 R¹ R³² R⁵⁹ 818 R² R³² R⁵⁹ 1301 R³² R³² R⁵⁹ 336 R¹ R³² R⁶⁰ 819 R² R³² R⁶⁰ 1302 R³² R³² R⁶⁰ 337 R¹ R³² R⁶¹ 820 R² R³² R⁶¹ 1303 R³² R³² R⁶¹ 338 R¹ R³² R⁶² 821 R² R³² R⁶² 1304 R³² R³² R⁶² 339 R¹ R³² R⁶³ 822 R² R³² R⁶³ 1305 R³² R³² R⁶³ 340 R¹ R³² R⁶⁴ 823 R² R³² R⁶⁴ 1306 R³² R³² R⁶⁴ 341 R¹ R³² R⁶⁵ 824 R² R³² R⁶⁵ 1307 R³² R³² R⁶⁵ 342 R¹ R³² R⁶⁶ 825 R² R³² R⁶⁶ 1308 R³² R³² R⁶⁶ 343 R¹ R³² R⁶⁷ 826 R² R³² R⁶⁷ 1309 R³² R³² R⁶⁷ 344 R¹ R³² R⁶⁸ 827 R² R³² R⁶⁸ 1310 R³² R³² R⁶⁸ 345 R¹ R³² R⁶⁹ 828 R² R³² R⁶⁹ 1311 R³² R³² R⁶⁹ 346 R¹ R³⁶ R¹  829 R² R³⁶ R¹  1312 R³² R³⁶ R¹  347 R¹ R³⁶ R²  830 R² R³⁶ R²  1313 R³² R³⁶ R²  348 R¹ R³⁶ R³  831 R² R³⁶ R³  1314 R³² R³⁶ R³  349 R¹ R³⁶ R⁴  832 R² R³⁶ R⁴  1315 R³² R³⁶ R⁴  350 R¹ R³⁶ R⁵  833 R² R³⁶ R⁵  1316 R³² R³⁶ R⁵  351 R¹ R³⁶ R⁶  834 R² R³⁶ R⁶  1317 R³² R³⁶ R⁶  352 R¹ R³⁶ R⁷  835 R² R³⁶ R⁷  1318 R³² R³⁶ R⁷  353 R¹ R³⁶ R⁸  836 R² R³⁶ R⁸  1319 R³² R³⁶ R⁸  354 R¹ R³⁶ R⁹  837 R² R³⁶ R⁹  1320 R³² R³⁶ R⁹  355 R¹ R³⁶ R¹⁰ 838 R² R³⁶ R¹⁰ 1321 R³² R³⁶ R¹⁰ 356 R¹ R³⁶ R¹¹ 839 R² R³⁶ R¹¹ 1322 R³² R³⁶ R¹¹ 357 R¹ R³⁶ R¹² 840 R² R³⁶ R¹² 1323 R³² R³⁶ R¹² 358 R¹ R³⁶ R¹³ 841 R² R³⁶ R¹³ 1324 R³² R³⁶ R¹³ 359 R¹ R³⁶ R¹⁴ 842 R² R³⁶ R¹⁴ 1325 R³² R³⁶ R¹⁴ 360 R¹ R³⁶ R¹⁵ 843 R² R³⁶ R¹⁵ 1326 R³² R³⁶ R¹⁵ 361 R¹ R³⁶ R¹⁶ 844 R² R³⁶ R¹⁶ 1327 R³² R³⁶ R¹⁶ 362 R¹ R³⁶ R¹⁷ 845 R² R³⁶ R¹⁷ 1328 R³² R³⁶ R¹⁷ 363 R¹ R³⁶ R¹⁸ 846 R² R³⁶ R¹⁸ 1329 R³² R³⁶ R¹⁸ 364 R¹ R³⁶ R¹⁹ 847 R² R³⁶ R¹⁹ 1330 R³² R³⁶ R¹⁹ 365 R¹ R³⁶ R²⁰ 848 R² R³⁶ R²⁰ 1331 R³² R³⁶ R²⁰ 366 R¹ R³⁶ R²¹ 849 R² R³⁶ R²¹ 1332 R³² R³⁶ R²¹ 367 R¹ R³⁶ R²² 850 R² R³⁶ R²² 1333 R³² R³⁶ R²² 368 R¹ R³⁶ R²³ 851 R² R³⁶ R²³ 1334 R³² R³⁶ R²³ 369 R¹ R³⁶ R²⁴ 852 R² R³⁶ R²⁴ 1335 R³² R³⁶ R²⁴ 370 R¹ R³⁶ R²⁵ 853 R² R³⁶ R²⁵ 1336 R³² R³⁶ R²⁵ 371 R¹ R³⁶ R²⁶ 854 R² R³⁶ R²⁶ 1337 R³² R³⁶ R²⁶ 372 R¹ R³⁶ R²⁷ 855 R² R³⁶ R²⁷ 1338 R³² R³⁶ R²⁷ 373 R¹ R³⁶ R²⁸ 856 R² R³⁶ R²⁸ 1339 R³² R³⁶ R²⁸ 374 R¹ R³⁶ R²⁹ 857 R² R³⁶ R²⁹ 1340 R³² R³⁶ R²⁹ 375 R¹ R³⁶ R³⁰ 858 R² R³⁶ R³⁰ 1341 R³² R³⁶ R³⁰ 376 R¹ R³⁶ R³¹ 859 R² R³⁶ R³¹ 1342 R³² R³⁶ R³¹ 377 R¹ R³⁶ R³² 860 R² R³⁶ R³² 1343 R³² R³⁶ R³² 378 R¹ R³⁶ R³³ 861 R² R³⁶ R³³ 1344 R³² R³⁶ R³³ 379 R¹ R³⁶ R³⁴ 862 R² R³⁶ R³⁴ 1345 R³² R³⁶ R³⁴ 380 R¹ R³⁶ R³⁵ 863 R² R³⁶ R³⁵ 1346 R³² R³⁶ R³⁵ 381 R¹ R³⁶ R³⁶ 864 R² R³⁶ R³⁶ 1347 R³² R³⁶ R³⁶ 382 R¹ R³⁶ R³⁷ 865 R² R³⁶ R³⁷ 1348 R³² R³⁶ R³⁷ 383 R¹ R³⁶ R³⁸ 866 R² R³⁶ R³⁸ 1349 R³² R³⁶ R³⁸ 384 R¹ R³⁶ R³⁹ 867 R² R³⁶ R³⁹ 1350 R³² R³⁶ R³⁹ 385 R¹ R³⁶ R⁴⁰ 868 R² R³⁶ R⁴⁰ 1351 R³² R³⁶ R⁴⁰ 386 R¹ R³⁶ R⁴¹ 869 R² R³⁶ R⁴¹ 1352 R³² R³⁶ R⁴¹ 387 R¹ R³⁶ R⁴² 870 R² R³⁶ R⁴² 1353 R³² R³⁶ R⁴² 388 R¹ R³⁶ R⁴³ 871 R² R³⁶ R⁴³ 1354 R³² R³⁶ R⁴³ 389 R¹ R³⁶ R⁴⁴ 872 R² R³⁶ R⁴⁴ 1355 R³² R³⁶ R⁴⁴ 390 R¹ R³⁶ R⁴⁵ 873 R² R³⁶ R⁴⁵ 1356 R³² R³⁶ R⁴⁵ 391 R¹ R³⁶ R⁴⁶ 874 R² R³⁶ R⁴⁶ 1357 R³² R³⁶ R⁴⁶ 392 R¹ R³⁶ R⁴⁷ 875 R² R³⁶ R⁴⁷ 1358 R³² R³⁶ R⁴⁷ 393 R¹ R³⁶ R⁴⁸ 876 R² R³⁶ R⁴⁸ 1359 R³² R³⁶ R⁴⁸ 394 R¹ R³⁶ R⁴⁹ 877 R² R³⁶ R⁴⁹ 1360 R³² R³⁶ R⁴⁹ 395 R¹ R³⁶ R⁵⁰ 878 R² R³⁶ R⁵⁰ 1361 R³² R³⁶ R⁵⁰ 396 R¹ R³⁶ R⁵¹ 879 R² R³⁶ R⁵¹ 1362 R³² R³⁶ R⁵¹ 397 R¹ R³⁶ R⁵² 880 R² R³⁶ R⁵² 1363 R³² R³⁶ R⁵² 398 R¹ R³⁶ R⁵³ 881 R² R³⁶ R⁵³ 1364 R³² R³⁶ R⁵³ 399 R¹ R³⁶ R⁵⁴ 882 R² R³⁶ R⁵⁴ 1365 R³² R³⁶ R⁵⁴ 400 R¹ R³⁶ R⁵⁵ 883 R² R³⁶ R⁵⁵ 1366 R³² R³⁶ R⁵⁵ 401 R¹ R³⁶ R⁵⁶ 884 R² R³⁶ R⁵⁶ 1367 R³² R³⁶ R⁵⁶ 402 R¹ R³⁶ R⁵⁷ 885 R² R³⁶ R⁵⁷ 1368 R³² R³⁶ R⁵⁷ 403 R¹ R³⁶ R⁵⁸ 886 R² R³⁶ R⁵⁸ 1369 R³² R³⁶ R⁵⁸ 404 R¹ R³⁶ R⁵⁹ 887 R² R³⁶ R⁵⁹ 1370 R³² R³⁶ R⁵⁹ 405 R¹ R³⁶ R⁶⁰ 888 R² R³⁶ R⁶⁰ 1371 R³² R³⁶ R⁶⁰ 406 R¹ R³⁶ R⁶¹ 889 R² R³⁶ R⁶¹ 1372 R³² R³⁶ R⁶¹ 407 R¹ R³⁶ R⁶² 890 R² R³⁶ R⁶² 1373 R³² R³⁶ R⁶² 408 R¹ R³⁶ R⁶³ 891 R² R³⁶ R⁶³ 1374 R³² R³⁶ R⁶³ 409 R¹ R³⁶ R⁶⁴ 892 R² R³⁶ R⁶⁴ 1375 R³² R³⁶ R⁶⁴ 410 R¹ R³⁶ R⁶⁵ 893 R² R³⁶ R⁶⁵ 1376 R³² R³⁶ R⁶⁵ 411 R¹ R³⁶ R⁶⁶ 894 R² R³⁶ R⁶⁶ 1377 R³² R³⁶ R⁶⁶ 412 R¹ R³⁶ R⁶⁷ 895 R² R³⁶ R⁶⁷ 1378 R³² R³⁶ R⁶⁷ 413 R¹ R³⁶ R⁶⁸ 896 R² R³⁶ R⁶⁸ 1379 R³² R³⁶ R⁶⁸ 414 R¹ R³⁶ R⁶⁹ 897 R² R³⁶ R⁶⁹ 1380 R³² R³⁶ R⁶⁹ 415 R¹ R⁴¹ R¹  898 R² R⁴¹ R¹  1381 R³² R⁴¹ R¹  416 R¹ R⁴¹ R²  899 R² R⁴¹ R²  1382 R³² R⁴¹ R²  417 R¹ R⁴¹ R³  900 R² R⁴¹ R³  1383 R³² R⁴¹ R³  418 R¹ R⁴¹ R⁴  901 R² R⁴¹ R⁴  1384 R³² R⁴¹ R⁴  419 R¹ R⁴¹ R⁵  902 R² R⁴¹ R⁵  1385 R³² R⁴¹ R⁵  420 R¹ R⁴¹ R⁶  903 R² R⁴¹ R⁶  1386 R³² R⁴¹ R⁶  421 R¹ R⁴¹ R⁷  904 R² R⁴¹ R⁷  1387 R³² R⁴¹ R⁷  422 R¹ R⁴¹ R⁸  905 R² R⁴¹ R⁸  1388 R³² R⁴¹ R⁸  423 R¹ R⁴¹ R⁹  906 R² R⁴¹ R⁹  1389 R³² R⁴¹ R⁹  424 R¹ R⁴¹ R¹⁰ 907 R² R⁴¹ R¹⁰ 1390 R³² R⁴¹ R¹⁰ 425 R¹ R⁴¹ R¹¹ 908 R² R⁴¹ R¹¹ 1391 R³² R⁴¹ R¹¹ 426 R¹ R⁴¹ R¹² 909 R² R⁴¹ R¹² 1392 R³² R⁴¹ R¹² 427 R¹ R⁴¹ R¹³ 910 R² R⁴¹ R¹³ 1393 R³² R⁴¹ R¹³ 428 R¹ R⁴¹ R¹⁴ 911 R² R⁴¹ R¹⁴ 1394 R³² R⁴¹ R¹⁴ 429 R¹ R⁴¹ R¹⁵ 912 R² R⁴¹ R¹⁵ 1395 R³² R⁴¹ R¹⁵ 430 R¹ R⁴¹ R¹⁶ 913 R² R⁴¹ R¹⁶ 1396 R³² R⁴¹ R¹⁶ 431 R¹ R⁴¹ R¹⁷ 914 R² R⁴¹ R¹⁷ 1397 R³² R⁴¹ R¹⁷ 432 R¹ R⁴¹ R¹⁸ 915 R² R⁴¹ R¹⁸ 1398 R³² R⁴¹ R¹⁸ 433 R¹ R⁴¹ R¹⁹ 916 R² R⁴¹ R¹⁹ 1399 R³² R⁴¹ R¹⁹ 434 R¹ R⁴¹ R²⁰ 917 R² R⁴¹ R²⁰ 1400 R³² R⁴¹ R²⁰ 435 R¹ R⁴¹ R²¹ 918 R² R⁴¹ R²¹ 1401 R³² R⁴¹ R²¹ 436 R¹ R⁴¹ R²² 919 R² R⁴¹ R²² 1402 R³² R⁴¹ R²² 437 R¹ R⁴¹ R²³ 920 R² R⁴¹ R²³ 1403 R³² R⁴¹ R²³ 438 R¹ R⁴¹ R²⁴ 921 R² R⁴¹ R²⁴ 1404 R³² R⁴¹ R²⁴ 439 R¹ R⁴¹ R²⁵ 922 R² R⁴¹ R²⁵ 1405 R³² R⁴¹ R²⁵ 440 R¹ R⁴¹ R²⁶ 923 R² R⁴¹ R²⁶ 1406 R³² R⁴¹ R²⁶ 441 R¹ R⁴¹ R²⁷ 924 R² R⁴¹ R²⁷ 1407 R³² R⁴¹ R²⁷ 442 R¹ R⁴¹ R²⁸ 925 R² R⁴¹ R²⁸ 1408 R³² R⁴¹ R²⁸ 443 R¹ R⁴¹ R²⁹ 926 R² R⁴¹ R²⁹ 1409 R³² R⁴¹ R²⁹ 444 R¹ R⁴¹ R³⁰ 927 R² R⁴¹ R³⁰ 1410 R³² R⁴¹ R³⁰ 445 R¹ R⁴¹ R³¹ 928 R² R⁴¹ R³¹ 1411 R³² R⁴¹ R³¹ 446 R¹ R⁴¹ R³² 929 R² R⁴¹ R³² 1412 R³² R⁴¹ R³² 447 R¹ R⁴¹ R³³ 930 R² R⁴¹ R³³ 1413 R³² R⁴¹ R³³ 448 R¹ R⁴¹ R³⁴ 931 R² R⁴¹ R³⁴ 1414 R³² R⁴¹ R³⁴ 449 R¹ R⁴¹ R³⁵ 932 R² R⁴¹ R³⁵ 1415 R³² R⁴¹ R³⁵ 450 R¹ R⁴¹ R³⁶ 933 R² R⁴¹ R³⁶ 1416 R³² R⁴¹ R³⁶ 451 R¹ R⁴¹ R³⁷ 934 R² R⁴¹ R³⁷ 1417 R³² R⁴¹ R³⁷ 452 R¹ R⁴¹ R³⁸ 935 R² R⁴¹ R³⁸ 1418 R³² R⁴¹ R³⁸ 453 R¹ R⁴¹ R³⁹ 936 R² R⁴¹ R³⁹ 1419 R³² R⁴¹ R³⁹ 454 R¹ R⁴¹ R⁴⁰ 937 R² R⁴¹ R⁴⁰ 1420 R³² R⁴¹ R⁴⁰ 455 R¹ R⁴¹ R⁴¹ 938 R² R⁴¹ R⁴¹ 1421 R³² R⁴¹ R⁴¹ 456 R¹ R⁴¹ R⁴² 939 R² R⁴¹ R⁴² 1422 R³² R⁴¹ R⁴² 457 R¹ R⁴¹ R⁴³ 940 R² R⁴¹ R⁴³ 1423 R³² R⁴¹ R⁴³ 458 R¹ R⁴¹ R⁴⁴ 941 R² R⁴¹ R⁴⁴ 1424 R³² R⁴¹ R⁴⁴ 459 R¹ R⁴¹ R⁴⁵ 942 R² R⁴¹ R⁴⁵ 1425 R³² R⁴¹ R⁴⁵ 460 R¹ R⁴¹ R⁴⁶ 943 R² R⁴¹ R⁴⁶ 1426 R³² R⁴¹ R⁴⁶ 461 R¹ R⁴¹ R⁴⁷ 944 R² R⁴¹ R⁴⁷ 1427 R³² R⁴¹ R⁴⁷ 462 R¹ R⁴¹ R⁴⁸ 945 R² R⁴¹ R⁴⁸ 1428 R³² R⁴¹ R⁴⁸ 463 R¹ R⁴¹ R⁴⁹ 946 R² R⁴¹ R⁴⁹ 1429 R³² R⁴¹ R⁴⁹ 464 R¹ R⁴¹ R⁵⁰ 947 R² R⁴¹ R⁵⁰ 1430 R³² R⁴¹ R⁵⁰ 465 R¹ R⁴¹ R⁵¹ 948 R² R⁴¹ R⁵¹ 1431 R³² R⁴¹ R⁵¹ 466 R¹ R⁴¹ R⁵² 949 R² R⁴¹ R⁵² 1432 R³² R⁴¹ R⁵² 467 R¹ R⁴¹ R⁵³ 950 R² R⁴¹ R⁵³ 1433 R³² R⁴¹ R⁵³ 468 R¹ R⁴¹ R⁵⁴ 951 R² R⁴¹ R⁵⁴ 1434 R³² R⁴¹ R⁵⁴ 469 R¹ R⁴¹ R⁵⁵ 952 R² R⁴¹ R⁵⁵ 1435 R³² R⁴¹ R⁵⁵ 470 R¹ R⁴¹ R⁵⁶ 953 R² R⁴¹ R⁵⁶ 1436 R³² R⁴¹ R⁵⁶ 471 R¹ R⁴¹ R⁵⁷ 954 R² R⁴¹ R⁵⁷ 1437 R³² R⁴¹ R⁵⁷ 472 R¹ R⁴¹ R⁵⁸ 955 R² R⁴¹ R⁵⁸ 1438 R³² R⁴¹ R⁵⁸ 473 R¹ R⁴¹ R⁵⁹ 956 R² R⁴¹ R⁵⁹ 1439 R³² R⁴¹ R⁵⁹ 474 R¹ R⁴¹ R⁶⁰ 957 R² R⁴¹ R⁶⁰ 1440 R³² R⁴¹ R⁶⁰ 475 R¹ R⁴¹ R⁶¹ 958 R² R⁴¹ R⁶¹ 1441 R³² R⁴¹ R⁶¹ 476 R¹ R⁴¹ R⁶² 959 R² R⁴¹ R⁶² 1442 R³² R⁴¹ R⁶² 477 R¹ R⁴¹ R⁶³ 960 R² R⁴¹ R⁶³ 1443 R³² R⁴¹ R⁶³ 478 R¹ R⁴¹ R⁶⁴ 961 R² R⁴¹ R⁶⁴ 1444 R³² R⁴¹ R⁶⁴ 479 R¹ R⁴¹ R⁶⁵ 962 R² R⁴¹ R⁶⁵ 1445 R³² R⁴¹ R⁶⁵ 480 R¹ R⁴¹ R⁶⁶ 963 R² R⁴¹ R⁶⁶ 1446 R³² R⁴¹ R⁶⁶ 481 R¹ R⁴¹ R⁶⁷ 964 R² R⁴¹ R⁶⁷ 1447 R³² R⁴¹ R⁶⁷ 482 R¹ R⁴¹ R⁶⁸ 965 R² R⁴¹ R⁶⁸ 1448 R³² R⁴¹ R⁶⁸ 483 R¹ R⁴¹ R⁶⁹ 966 R² R⁴¹ R⁶⁹ 1449 R³² R⁴¹ R⁶⁹ where R¹ to R⁶⁹ have the following structures:

In some embodiments of the compound whose ligand L_(X) has the structure of Formula IV, the compound has a formula of M(L_(A))_(x)(L_(B))_(y)(L_(C))_(z) where each one of L_(B) and L_(C) is a bidentate ligand; and where x is 1, 2, or 3; y is 0, 1, or 2; z is 0, 1, or 2; and x+y+z is the oxidation state of the metal M. In some embodiments, the compound has a formula selected from the group consisting of Ir(L_(A))₃, Ir(L_(A))(L_(B))₂, Ir(L_(A))₂(L_(B)), Ir(L_(A))₂(L_(C)), and Ir(L_(A))(L_(B))(L_(C)); and where L_(A), L_(B), and L_(C) are different from each other; or the compound has a formula of Pt(L_(A))(L_(B)); and where L_(A) and L_(B) can be same or different. In some embodiments, L_(B) and L_(C) are each independently selected from the group consisting of

where, each X¹ to X¹³ are independently selected from the group consisting of C and N; X is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″; R′ and R″ are optionally fused or joined to form a ring; each R_(a), R_(b), R_(c), and R_(d) may represent from mono substitution to the maximum possible number of substitutions, or no substitution; R′, R″, R_(a), R_(b), R_(c), and R_(d) are each independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and where any two adjacent substitutents of R_(a), R_(b), R_(c), and R_(d) are optionally fused or joined to form a ring or form a multidentate ligand.

In some embodiments, L_(B) is selected from the group consisting of L_(B1) to L_(B263) having the following structures:

In some embodiments, L_(B) is selected from the group consisting of: L_(B1), L_(B2), L_(B18), L_(B28), L_(B38), L_(B108), L_(B118), L_(B122), L_(B124), L_(B126), L_(B128), L_(B130), L_(B32), L_(B134), L_(B136), L_(B138), L_(B140), L_(B142), L_(B144), L_(B156), L_(B58), L_(B160), L_(B162), L_(B164), L_(B168), L_(B172), L_(B175), L_(B204), L_(B206), L_(B214), L_(B216), L_(B218), L_(B220), L_(B222), L_(B231), L_(B233), L_(B235), L_(B237), L_(B240), L_(B242), L_(B244), L_(B246), L_(B248), L_(B250), L_(B252), L_(B254), L_(B256), L_(B258), L_(B260), L_(B262), and L_(B263).

In some embodiments, L_(B) is selected from the group consisting of: L_(B1), L_(B2), L_(B18), L_(B28), L_(B38), L_(B108), L_(B118), L_(B122), L_(B124), L_(B126), L_(B128), L_(B32), L_(B136), L_(B138), L_(B142), L_(B156), L_(B162), L_(B204), L_(B206), L_(B214), L_(B216), L_(B218), L_(B220), L_(B231), L_(B233), and L_(B237).

In some embodiments, L_(C) has the structure of L_(Cj-1), where j is an integer from 1 to 768, having the structures based on a structure of

or L_(C) has the structure of L_(Cj-II), where j is an integer from 1 to 768, having the structures based on a structure of

where, for each L_(Cj) in L_(Cj-I) and L_(Cj-II), R¹ and R² are defined as provided below:

L_(Cj) R¹ R² L_(C1) R^(D1) R^(D1) L_(C2) R^(D2) R^(D2) L_(C3) R^(D3) R^(D3) L_(C4) R^(D4) R^(D4) L_(C5) R^(D5) R^(D5) L_(C6) R^(D6) R^(D6) L_(C7) R^(D7) R^(D7) L_(C8) R^(D8) R^(D8) L_(C9) R^(D9) R^(D9) L_(C10) R^(D10) R^(D10) L_(C11) R^(D11) R^(D11) L_(C12) R^(D12) R^(D12) L_(C13) R^(D13) R^(D13) L_(C14) R^(D14) R^(D14) L_(C15) R^(D15) R^(D15) L_(C16) R^(D16) R^(D16) L_(C17) R^(D17) R^(D17) L_(C18) R^(D18) R^(D18) L_(C19) R^(D19) R^(D19) L_(C20) R^(D20) R^(D20) L_(C21) R^(D21) R^(D21) L_(C22) R^(D22) R^(D22) L_(C23) R^(D23) R^(D23) L_(C24) R^(D24) R^(D24) L_(C25) R^(D25) R^(D25) L_(C26) R^(D26) R^(D26) L_(C27) R^(D27) R^(D27) L_(C28) R^(D28) R^(D28) L_(C29) R^(D29) R^(D29) L_(C30) R^(D30) R^(D30) L_(C31) R^(D31) R^(D31) L_(C32) R^(D32) R^(D32) L_(C33) R^(D33) R^(D33) L_(C34) R^(D34) R^(D34) L_(C35) R^(D35) R^(D35) L_(C36) R^(D36) R^(D36) L_(C37) R^(D37) R^(D37) L_(C38) R^(D38) R^(D38) L_(C39) R^(D39) R^(D39) L_(C40) R^(D40) R^(D40) L_(C41) R^(D41) R^(D41) L_(C42) R^(D42) R^(D42) L_(C43) R^(D43) R^(D43) L_(C44) R^(D44) R^(D44) L_(C45) R^(D45) R^(D45) L_(C46) R^(D46) R^(D46) L_(C47) R^(D47) R^(D47) L_(C48) R^(D48) R^(D48) L_(C49) R^(D49) R^(D49) L_(C50) R^(D50) R^(D50) L_(C51) R^(D51) R^(D51) L_(C52) R^(D52) R^(D52) L_(C53) R^(D53) R^(D53) L_(C54) R^(D54) R^(D54) L_(C55) R^(D55) R^(D55) L_(C56) R^(D56) R^(D56) L_(C57) R^(D57) R^(D57) L_(C58) R^(D58) R^(D58) L_(C59) R^(D59) R^(D59) L_(C60) R^(D60) R^(D60) L_(C61) R^(D61) R^(D61) L_(C62) R^(D62) R^(D62) L_(C63) R^(D63) R^(D63) L_(C64) R^(D64) R^(D64) L_(C65) R^(D65) R^(D65) L_(C66) R^(D66) R^(D66) L_(C67) R^(D67) R^(D67) L_(C68) R^(D68) R^(D68) L_(C69) R^(D69) R^(D69) L_(C70) R^(D70) R^(D70) L_(C71) R^(D71) R^(D71) L_(C72) R^(D72) R^(D72) L_(C73) R^(D73) R^(D73) L_(C74) R^(D74) R^(D74) L_(C75) R^(D75) R^(D75) L_(C76) R^(D76) R^(D76) L_(C77) R^(D77) R^(D77) L_(C78) R^(D78) R^(D78) L_(C79) R^(D79) R^(D79) L_(C80) R^(D80) R^(D80) L_(C81) R^(D81) R^(D81) L_(C82) R^(D82) R^(D82) L_(C83) R^(D83) R^(D83) L_(C84) R^(D84) R^(D84) L_(C85) R^(D85) R^(D85) L_(C86) R^(D86) R^(D86) L_(C87) R^(D87) R^(D87) L_(C88) R^(D88) R^(D88) L_(C89) R^(D89) R^(D89) L_(C90) R^(D90) R^(D90) L_(C91) R^(D91) R^(D91) L_(C92) R^(D92) R^(D92) L_(C93) R^(D93) R^(D93) L_(C94) R^(D94) R^(D94) L_(C95) R^(D95) R^(D95) L_(C96) R^(D96) R^(D96) L_(C97) R^(D97) R^(D97) L_(C98) R^(D98) R^(D98) L_(C99) R^(D99) R^(D99) L_(C100) R^(D100) R^(D100) L_(C101) R^(D101) R^(D101) L_(C102) R^(D102) R^(D102) L_(C103) R^(D103) R^(D103) L_(C104) R^(D104) R^(D104) L_(C105) R^(D105) R^(D105) L_(C106) R^(D106) R^(D106) L_(C107) R^(D107) R^(D107) L_(C108) R^(D108) R^(D108) L_(C109) R^(D109) R^(D109) L_(C110) R^(D110) R^(D110) L_(C111) R^(D111) R^(D111) L_(C112) R^(D112) R^(D112) L_(C113) R^(D113) R^(D113) L_(C114) R^(D114) R^(D114) L_(C115) R^(D115) R^(D115) L_(C116) R^(D116) R^(D116) L_(C117) R^(D117) R^(D117) L_(C118) R^(D118) R^(D118) L_(C119) R^(D119) R^(D119) L_(C120) R^(D120) R^(D120) L_(C121) R^(D121) R^(D121) L_(C122) R^(D122) R^(D122) L_(C123) R^(D123) R^(D123) L_(C124) R^(D124) R^(D124) L_(C125) R^(D125) R^(D125) L_(C126) R^(D126) R^(D126) L_(C127) R^(D127) R^(D127) L_(C128) R^(D128) R^(D128) L_(C129) R^(D129) R^(D129) L_(C130) R^(D130) R^(D130) L_(C131) R^(D131) R^(D131) L_(C132) R^(D132) R^(D132) L_(C133) R^(D133) R^(D133) L_(C134) R^(D134) R^(D134) L_(C135) R^(D135) R^(D135) L_(C136) R^(D136) R^(D136) L_(C137) R^(D137) R^(D137) L_(C138) R^(D138) R^(D138) L_(C139) R^(D139) R^(D139) L_(C140) R^(D140) R^(D140) L_(C141) R^(D141) R^(D141) L_(C142) R^(D142) R^(D142) L_(C143) R^(D143) R^(D143) L_(C144) R^(D144) R^(D144) L_(C145) R^(D145) R^(D145) L_(C146) R^(D146) R^(D146) L_(C147) R^(D147) R^(D147) L_(C148) R^(D148) R^(D148) L_(C149) R^(D149) R^(D149) L_(C150) R^(D150) R^(D150) L_(C151) R^(D151) R^(D151) L_(C152) R^(D152) R^(D152) L_(C153) R^(D153) R^(D153) L_(C154) R^(D154) R^(D154) L_(C155) R^(D155) R^(D155) L_(C156) R^(D156) R^(D156) L_(C157) R^(D157) R^(D157) L_(C158) R^(D158) R^(D158) L_(C159) R^(D159) R^(D159) L_(C160) R^(D160) R^(D160) L_(C161) R^(D161) R^(D161) L_(C162) R^(D162) R^(D162) L_(C163) R^(D163) R^(D163) L_(C164) R^(D164) R^(D164) L_(C165) R^(D165) R^(D165) L_(C166) R^(D166) R^(D166) L_(C167) R^(D167) R^(D167) L_(C168) R^(D168) R^(D168) L_(C169) R^(D169) R^(D169) L_(C170) R^(D170) R^(D170) L_(C171) R^(D171) R^(D171) L_(C172) R^(D172) R^(D172) L_(C173) R^(D173) R^(D173) L_(C174) R^(D174) R^(D174) L_(C175) R^(D175) R^(D175) L_(C176) R^(D176) R^(D176) L_(C177) R^(D177) R^(D177) L_(C178) R^(D178) R^(D178) L_(C179) R^(D179) R^(D179) L_(C180) R^(D180) R^(D180) L_(C181) R^(D181) R^(D181) L_(C182) R^(D182) R^(D182) L_(C183) R^(D183) R^(D183) L_(C184) R^(D184) R^(D184) L_(C185) R^(D185) R^(D185) L_(C186) R^(D186) R^(D186) L_(C187) R^(D187) R^(D187) L_(C188) R^(D188) R^(D188) L_(C189) R^(D189) R^(D189) L_(C190) R^(D190) R^(D190) L_(C191) R^(D191) R^(D191) L_(C192) R^(D192) R^(D192) L_(C193) R^(D1) R^(D3) L_(C194) R^(D1) R^(D4) L_(C195) R^(D1) R^(D5) L_(C196) R^(D1) R^(D9) L_(C197) R^(D1) R^(D10) L_(C198) R^(D1) R^(D17) L_(C199) R^(D1) R^(D18) L_(C200) R^(D1) R^(D20) L_(C201) R^(D1) R^(D22) L_(C202) R^(D1) R^(D37) L_(C203) R^(D1) R^(D40) L_(C204) R^(D1) R^(D41) L_(C205) R^(D1) R^(D42) L_(C206) R^(D1) R^(D43) L_(C207) R^(D1) R^(D48) L_(C208) R^(D1) R^(D49) L_(C209) R^(D1) R^(D50) L_(C210) R^(D1) R^(D54) L_(C211) R^(D1) R^(D55) L_(C212) R^(D1) R^(D58) L_(C213) R^(D1) R^(D59) L_(C214) R^(D1) R^(D78) L_(C215) R^(D1) R^(D79) L_(C216) R^(D1) R^(D81) L_(C217) R^(D1) R^(D87) L_(C218) R^(D1) R^(D88) L_(C219) R^(D1) R^(D89) L_(C220) R^(D1) R^(D93) L_(C221) R^(D1) R^(D116) L_(C222) R^(D1) R^(D117) L_(C223) R^(D1) R^(D118) L_(C224) R^(D1) R^(D119) L_(C225) R^(D1) R^(D120) L_(C226) R^(D1) R^(D133) L_(C227) R^(D1) R^(D134) L_(C228) R^(D1) R^(D135) L_(C229) R^(D1) R^(D136) L_(C230) R^(D1) R^(D143) L_(C231) R^(D1) R^(D144) L_(C232) R^(D1) R^(D145) L_(C233) R^(D1) R^(D146) L_(C234) R^(D1) R^(D147) L_(C235) R^(D1) R^(D149) L_(C236) R^(D1) R^(D151) L_(C237) R^(D1) R^(D154) L_(C238) R^(D1) R^(D155) L_(C239) R^(D1) R^(D161) L_(C240) R^(D1) R^(D175) L_(C241) R^(D4) R^(D3) L_(C242) R^(D4) R^(D5) L_(C243) R^(D4) R^(D9) L_(C244) R^(D4) R^(D10) L_(C245) R^(D4) R^(D17) L_(C246) R^(D4) R^(D18) L_(C247) R^(D4) R^(D20) L_(C248) R^(D4) R^(D22) L_(C249) R^(D4) R^(D37) L_(C250) R^(D4) R^(D40) L_(C251) R^(D4) R^(D41) L_(C252) R^(D4) R^(D42) L_(C253) R^(D4) R^(D43) L_(C254) R^(D4) R^(D48) L_(C255) R^(D4) R^(D49) L_(C256) R^(D4) R^(D50) L_(C257) R^(D4) R^(D54) L_(C258) R^(D4) R^(D55) L_(C259) R^(D4) R^(D58) L_(C260) R^(D4) R^(D59) L_(C261) R^(D4) R^(D78) L_(C262) R^(D4) R^(D79) L_(C263) R^(D4) R^(D81) L_(C264) R^(D4) R^(D87) L_(C265) R^(D4) R^(D88) L_(C266) R^(D4) R^(D89) L_(C267) R^(D4) R^(D93) L_(C268) R^(D4) R^(D116) L_(C269) R^(D4) R^(D117) L_(C270) R^(D4) R^(D118) L_(C271) R^(D4) R^(D119) L_(C272) R^(D4) R^(D120) L_(C273) R^(D4) R^(D133) L_(C274) R^(D4) R^(D134) L_(C275) R^(D4) R^(D135) L_(C276) R^(D4) R^(D136) L_(C277) R^(D4) R^(D143) L_(C278) R^(D4) R^(D144) L_(C279) R^(D4) R^(D145) L_(C280) R^(D4) R^(D146) L_(C281) R^(D4) R^(D147) L_(C282) R^(D4) R^(D149) L_(C283) R^(D4) R^(D151) L_(C284) R^(D4) R^(D154) L_(C285) R^(D4) R^(D155) L_(C286) R^(D4) R^(D161) L_(C287) R^(D4) R^(D175) L_(C288) R^(D9) R^(D3) L_(C289) R^(D9) R^(D5) L_(C290) R^(D9) R^(D10) L_(C291) R^(D9) R^(D17) L_(C292) R^(D9) R^(D18) L_(C293) R^(D9) R^(D20) L_(C294) R^(D9) R^(D22) L_(C295) R^(D9) R^(D37) L_(C296) R^(D9) R^(D40) L_(C297) R^(D9) R^(D41) L_(C298) R^(D9) R^(D42) L_(C299) R^(D9) R^(D43) L_(C300) R^(D9) R^(D48) L_(C301) R^(D9) R^(D49) L_(C302) R^(D9) R^(D50) L_(C303) R^(D9) R^(D54) L_(C304) R^(D9) R^(D55) L_(C305) R^(D9) R^(D58) L_(C306) R^(D9) R^(D59) L_(C307) R^(D9) R^(D78) L_(C308) R^(D9) R^(D79) L_(C309) R^(D9) R^(D81) L_(C310) R^(D9) R^(D87) L_(C311) R^(D9) R^(D88) L_(C312) R^(D9) R^(D89) L_(C313) R^(D9) R^(D93) L_(C314) R^(D9) R^(D116) L_(C315) R^(D9) R^(D117) L_(C316) R^(D9) R^(D118) L_(C317) R^(D9) R^(D119) L_(C318) R^(D9) R^(D120) L_(C319) R^(D9) R^(D133) L_(C320) R^(D9) R^(D134) L_(C321) R^(D9) R^(D135) L_(C322) R^(D9) R^(D136) L_(C323) R^(D9) R^(D143) L_(C324) R^(D9) R^(D144) L_(C325) R^(D9) R^(D145) L_(C326) R^(D9) R^(D146) L_(C327) R^(D9) R^(D147) L_(C328) R^(D9) R^(D149) L_(C329) R^(D9) R^(D151) L_(C330) R^(D9) R^(D154) L_(C331) R^(D9) R^(D155) L_(C332) R^(D9) R^(D161) L_(C333) R^(D9) R^(D175) L_(C334) R^(D10) R^(D3) L_(C335) R^(D10) R^(D5) L_(C336) R^(D10) R^(D17) L_(C337) R^(D10) R^(D18) L_(C338) R^(D10) R^(D20) L_(C339) R^(D10) R^(D22) L_(C340) R^(D10) R^(D37) L_(C341) R^(D10) R^(D40) L_(C342) R^(D10) R^(D41) L_(C343) R^(D10) R^(D42) L_(C344) R^(D10) R^(D43) L_(C345) R^(D10) R^(D48) L_(C346) R^(D10) R^(D49) L_(C347) R^(D10) R^(D50) L_(C348) R^(D10) R^(D54) L_(C349) R^(D10) R^(D55) L_(C350) R^(D10) R^(D58) L_(C351) R^(D10) R^(D59) L_(C352) R^(D10) R^(D78) L_(C353) R^(D10) R^(D79) L_(C354) R^(D10) R^(D81) L_(C355) R^(D10) R^(D87) L_(C356) R^(D10) R^(D88) L_(C357) R^(D10) R^(D89) L_(C358) R^(D10) R^(D93) L_(C359) R^(D10) R^(D116) L_(C360) R^(D10) R^(D117) L_(C361) R^(D10) R^(D118) L_(C362) R^(D10) R^(D119) L_(C363) R^(D10) R^(D120) L_(C364) R^(D10) R^(D133) L_(C365) R^(D10) R^(D134) L_(C366) R^(D10) R^(D135) L_(C367) R^(D10) R^(D136) L_(C368) R^(D10) R^(D143) L_(C369) R^(D10) R^(D144) L_(C370) R^(D10) R^(D145) L_(C371) R^(D10) R^(D146) L_(C372) R^(D10) R^(D147) L_(C373) R^(D10) R^(D149) L_(C374) R^(D10) R^(D151) L_(C375) R^(D10) R^(D154) L_(C376) R^(D10) R^(D155) L_(C377) R^(D10) R^(D161) L_(C378) R^(D10) R^(D175) L_(C379) R^(D17) R^(D3) L_(C380) R^(D17) R^(D5) L_(C381) R^(D17) R^(D18) L_(C382) R^(D17) R^(D20) L_(C383) R^(D17) R^(D22) L_(C384) R^(D17) R^(D37) L_(C385) R^(D17) R^(D40) L_(C386) R^(D17) R^(D41) L_(C387) R^(D17) R^(D42) L_(C388) R^(D17) R^(D43) L_(C389) R^(D17) R^(D48) L_(C390) R^(D17) R^(D49) L_(C391) R^(D17) R^(D50) L_(C392) R^(D17) R^(D54) L_(C393) R^(D17) R^(D55) L_(C394) R^(D17) R^(D58) L_(C395) R^(D17) R^(D59) L_(C396) R^(D17) R^(D78) L_(C397) R^(D17) R^(D79) L_(C398) R^(D17) R^(D81) L_(C399) R^(D17) R^(D87) L_(C400) R^(D17) R^(D88) L_(C401) R^(D17) R^(D89) L_(C402) R^(D17) R^(D93) L_(C403) R^(D17) R^(D116) L_(C404) R^(D17) R^(D117) L_(C405) R^(D17) R^(D118) L_(C406) R^(D17) R^(D119) L_(C407) R^(D17) R^(D120) L_(C408) R^(D17) R^(D133) L_(C409) R^(D17) R^(D134) L_(C410) R^(D17) R^(D135) L_(C411) R^(D17) R^(D136) L_(C412) R^(D17) R^(D143) L_(C413) R^(D17) R^(D144) L_(C414) R^(D17) R^(D145) L_(C415) R^(D17) R^(D146) L_(C416) R^(D17) R^(D147) L_(C417) R^(D17) R^(D149) L_(C418) R^(D17) R^(D151) L_(C419) R^(D17) R^(D154) L_(C420) R^(D17) R^(D155) L_(C421) R^(D17) R^(D161) L_(C422) R^(D17) R^(D175) L_(C423) R^(D50) R^(D3) L_(C424) R^(D50) R^(D5) L_(C425) R^(D50) R^(D18) L_(C426) R^(D50) R^(D20) L_(C427) R^(D50) R^(D22) L_(C428) R^(D50) R^(D37) L_(C429) R^(D50) R^(D40) L_(C430) R^(D50) R^(D41) L_(C431) R^(D50) R^(D42) L_(C432) R^(D50) R^(D43) L_(C433) R^(D50) R^(D48) L_(C434) R^(D50) R^(D49) L_(C435) R^(D50) R^(D54) L_(C436) R^(D50) R^(D55) L_(C437) R^(D50) R^(D58) L_(C438) R^(D50) R^(D59) L_(C439) R^(D50) R^(D78) L_(C440) R^(D50) R^(D79) L_(C441) R^(D50) R^(D81) L_(C442) R^(D50) R^(D87) L_(C443) R^(D50) R^(D88) L_(C444) R^(D50) R^(D89) L_(C445) R^(D50) R^(D93) L_(C446) R^(D50) R^(D116) L_(C447) R^(D50) R^(D117) L_(C448) R^(D50) R^(D118) L_(C449) R^(D50) R^(D119) L_(C450) R^(D50) R^(D120) L_(C451) R^(D50) R^(D133) L_(C452) R^(D50) R^(D134) L_(C453) R^(D50) R^(D135) L_(C454) R^(D50) R^(D136) L_(C455) R^(D50) R^(D143) L_(C456) R^(D50) R^(D144) L_(C457) R^(D50) R^(D145) L_(C458) R^(D50) R^(D146) L_(C459) R^(D50) R^(D147) L_(C460) R^(D50) R^(D149) L_(C461) R^(D50) R^(D151) L_(C462) R^(D50) R^(D154) L_(C463) R^(D50) R^(D155) L_(C464) R^(D50) R^(D161) L_(C465) R^(D50) R^(D175) L_(C466) R^(D55) R^(D3) L_(C467) R^(D55) R^(D5) L_(C468) R^(D55) R^(D18) L_(C469) R^(D55) R^(D20) L_(C470) R^(D55) R^(D22) L_(C471) R^(D55) R^(D37) L_(C472) R^(D55) R^(D40) L_(C473) R^(D55) R^(D41) L_(C474) R^(D55) R^(D42) L_(C475) R^(D55) R^(D43) L_(C476) R^(D55) R^(D48) L_(C477) R^(D55) R^(D49) L_(C478) R^(D55) R^(D54) L_(C479) R^(D55) R^(D58) L_(C480) R^(D55) R^(D59) L_(C481) R^(D55) R^(D78) L_(C482) R^(D55) R^(D79) L_(C483) R^(D55) R^(D81) L_(C484) R^(D55) R^(D87) L_(C485) R^(D55) R^(D88) L_(C486) R^(D55) R^(D89) L_(C487) R^(D55) R^(D93) L_(C488) R^(D55) R^(D116) L_(C489) R^(D55) R^(D117) L_(C490) R^(D55) R^(D118) L_(C491) R^(D55) R^(D119) L_(C492) R^(D55) R^(D120) L_(C493) R^(D55) R^(D133) L_(C494) R^(D55) R^(D134) L_(C495) R^(D55) R^(D135) L_(C496) R^(D55) R^(D136) L_(C497) R^(D55) R^(D143) L_(C498) R^(D55) R^(D144) L_(C499) R^(D55) R^(D145) L_(C500) R^(D55) R^(D146) L_(C501) R^(D55) R^(D147) L_(C502) R^(D55) R^(D149) L_(C503) R^(D55) R^(D151) L_(C504) R^(D55) R^(D154) L_(C505) R^(D55) R^(D155) L_(C506) R^(D55) R^(D161) L_(C507) R^(D55) R^(D175) L_(C508) R^(D116) R^(D3) L_(C509) R^(D116) R^(D5) L_(C510) R^(D116) R^(D17) L_(C511) R^(D116) R^(D18) L_(C512) R^(D116) R^(D20) L_(C513) R^(D116) R^(D22) L_(C514) R^(D116) R^(D37) L_(C515) R^(D116) R^(D40) L_(C516) R^(D116) R^(D41) L_(C517) R^(D116) R^(D42) L_(C518) R^(D116) R^(D43) L_(C519) R^(D116) R^(D48) L_(C520) R^(D116) R^(D49) L_(C521) R^(D116) R^(D54) L_(C522) R^(D116) R^(D58) L_(C523) R^(D116) R^(D59) L_(C524) R^(D116) R^(D78) L_(C525) R^(D116) R^(D79) L_(C526) R^(D116) R^(D81) L_(C527) R^(D116) R^(D87) L_(C528) R^(D116) R^(D88) L_(C529) R^(D116) R^(D89) L_(C530) R^(D116) R^(D93) L_(C531) R^(D116) R^(D117) L_(C532) R^(D116) R^(D118) L_(C533) R^(D116) R^(D119) L_(C534) R^(D116) R^(D120) L_(C535) R^(D116) R^(D133) L_(C536) R^(D116) R^(D134) L_(C537) R^(D116) R^(D135) L_(C538) R^(D116) R^(D136) L_(C539) R^(D116) R^(D143) L_(C540) R^(D116) R^(D144) L_(C541) R^(D116) R^(D145) L_(C542) R^(D116) R^(D146) L_(C543) R^(D116) R^(D147) L_(C544) R^(D116) R^(D149) L_(C545) R^(D116) R^(D151) L_(C546) R^(D116) R^(D154) L_(C547) R^(D116) R^(D155) L_(C548) R^(D116) R^(D161) L_(C549) R^(D116) R^(D175) L_(C550) R^(D143) R^(D3) L_(C551) R^(D143) R^(D5) L_(C552) R^(D143) R^(D17) L_(C553) R^(D143) R^(D18) L_(C554) R^(D143) R^(D20) L_(C555) R^(D143) R^(D22) L_(C556) R^(D143) R^(D37) L_(C557) R^(D143) R^(D40) L_(C558) R^(D143) R^(D41) L_(C559) R^(D143) R^(D42) L_(C560) R^(D143) R^(D43) L_(C561) R^(D143) R^(D48) L_(C562) R^(D143) R^(D49) L_(C563) R^(D143) R^(D54) L_(C564) R^(D143) R^(D58) L_(C565) R^(D143) R^(D59) L_(C566) R^(D143) R^(D78) L_(C567) R^(D143) R^(D79) L_(C568) R^(D143) R^(D81) L_(C569) R^(D143) R^(D87) L_(C570) R^(D143) R^(D88) L_(C571) R^(D143) R^(D89) L_(C572) R^(D143) R^(D93) L_(C573) R^(D143) R^(D116) L_(C574) R^(D143) R^(D117) L_(C575) R^(D143) R^(D118) L_(C576) R^(D143) R^(D119) L_(C577) R^(D143) R^(D120) L_(C578) R^(D143) R^(D133) L_(C579) R^(D143) R^(D134) L_(C580) R^(D143) R^(D135) L_(C581) R^(D143) R^(D136) L_(C582) R^(D143) R^(D144) L_(C583) R^(D143) R^(D145) L_(C584) R^(D143) R^(D146) L_(C585) R^(D143) R^(D147) L_(C586) R^(D143) R^(D149) L_(C587) R^(D143) R^(D151) L_(C588) R^(D143) R^(D154) L_(C589) R^(D143) R^(D155) L_(C590) R^(D143) R^(D161) L_(C591) R^(D143) R^(D175) L_(C592) R^(D144) R^(D3) L_(C593) R^(D144) R^(D5) L_(C594) R^(D144) R^(D17) L_(C595) R^(D144) R^(D18) L_(C596) R^(D144) R^(D20) L_(C597) R^(D144) R^(D22) L_(C598) R^(D144) R^(D37) L_(C599) R^(D144) R^(D40) L_(C600) R^(D144) R^(D41) L_(C601) R^(D144) R^(D42) L_(C602) R^(D144) R^(D43) L_(C603) R^(D144) R^(D48) L_(C604) R^(D144) R^(D49) L_(C605) R^(D144) R^(D54) L_(C606) R^(D144) R^(D58) L_(C607) R^(D144) R^(D59) L_(C608) R^(D144) R^(D78) L_(C609) R^(D144) R^(D79) L_(C610) R^(D144) R^(D81) L_(C611) R^(D144) R^(D87) L_(C612) R^(D144) R^(D88) L_(C613) R^(D144) R^(D89) L_(C614) R^(D144) R^(D93) L_(C615) R^(D144) R^(D116) L_(C616) R^(D144) R^(D117) L_(C617) R^(D144) R^(D118) L_(C618) R^(D144) R^(D119) L_(C619) R^(D144) R^(D120) L_(C620) R^(D144) R^(D133) L_(C621) R^(D144) R^(D134) L_(C622) R^(D144) R^(D135) L_(C623) R^(D144) R^(D136) L_(C624) R^(D144) R^(D145) L_(C625) R^(D144) R^(D146) L_(C626) R^(D144) R^(D147) L_(C627) R^(D144) R^(D149) L_(C628) R^(D144) R^(D151) L_(C629) R^(D144) R^(D154) L_(C630) R^(D144) R^(D155) L_(C631) R^(D144) R^(D161) L_(C632) R^(D144) R^(D175) L_(C633) R^(D145) R^(D3) L_(C634) R^(D145) R^(D5) L_(C635) R^(D145) R^(D17) L_(C636) R^(D145) R^(D18) L_(C637) R^(D145) R^(D20) L_(C638) R^(D145) R^(D22) L_(C639) R^(D145) R^(D37) L_(C640) R^(D145) R^(D40) L_(C641) R^(D145) R^(D41) L_(C642) R^(D145) R^(D42) L_(C643) R^(D145) R^(D43) L_(C644) R^(D145) R^(D48) L_(C645) R^(D145) R^(D49) L_(C646) R^(D145) R^(D54) L_(C647) R^(D145) R^(D58) L_(C648) R^(D145) R^(D59) L_(C649) R^(D145) R^(D78) L_(C650) R^(D145) R^(D79) L_(C651) R^(D145) R^(D81) L_(C652) R^(D145) R^(D87) L_(C653) R^(D145) R^(D88) L_(C654) R^(D145) R^(D89) L_(C655) R^(D145) R^(D93) L_(C656) R^(D145) R^(D116) L_(C657) R^(D145) R^(D117) L_(C658) R^(D145) R^(D118) L_(C659) R^(D145) R^(D119) L_(C660) R^(D145) R^(D120) L_(C661) R^(D145) R^(D133) L_(C662) R^(D145) R^(D134) L_(C663) R^(D145) R^(D135) L_(C664) R^(D145) R^(D136) L_(C665) R^(D145) R^(D146) L_(C666) R^(D145) R^(D147) L_(C667) R^(D145) R^(D149) L_(C668) R^(D145) R^(D151) L_(C669) R^(D145) R^(D154) L_(C670) R^(D145) R^(D155) L_(C671) R^(D145) R^(D161) L_(C672) R^(D145) R^(D175) L_(C673) R^(D146) R^(D3) L_(C674) R^(D146) R^(D5) L_(C675) R^(D146) R^(D17) L_(C676) R^(D146) R^(D18) L_(C677) R^(D146) R^(D20) L_(C678) R^(D146) R^(D22) L_(C679) R^(D146) R^(D37) L_(C680) R^(D146) R^(D40) L_(C681) R^(D146) R^(D41) L_(C682) R^(D146) R^(D42) L_(C683) R^(D146) R^(D43) L_(C684) R^(D146) R^(D48) L_(C685) R^(D146) R^(D49) L_(C686) R^(D146) R^(D54) L_(C687) R^(D146) R^(D58) L_(C688) R^(D146) R^(D59) L_(C689) R^(D146) R^(D78) L_(C690) R^(D146) R^(D79) L_(C691) R^(D146) R^(D81) L_(C692) R^(D146) R^(D87) L_(C693) R^(D146) R^(D88) L_(C694) R^(D146) R^(D89) L_(C695) R^(D146) R^(D93) L_(C696) R^(D146) R^(D117) L_(C697) R^(D146) R^(D118) L_(C698) R^(D146) R^(D119) L_(C699) R^(D146) R^(D120) L_(C700) R^(D146) R^(D133) L_(C701) R^(D146) R^(D134) L_(C702) R^(D146) R^(D135) L_(C703) R^(D146) R^(D136) L_(C704) R^(D146) R^(D146) L_(C705) R^(D146) R^(D147) L_(C706) R^(D146) R^(D149) L_(C707) R^(D146) R^(D151) L_(C708) R^(D146) R^(D154) L_(C709) R^(D146) R^(D155) L_(C710) R^(D146) R^(D161) L_(C711) R^(D146) R^(D175) L_(C712) R^(D133) R^(D3) L_(C713) R^(D133) R^(D5) L_(C714) R^(D133) R^(D3) L_(C715) R^(D133) R^(D18) L_(C716) R^(D133) R^(D20) L_(C717) R^(D133) R^(D22) L_(C718) R^(D133) R^(D37) L_(C719) R^(D133) R^(D40) L_(C720) R^(D133) R^(D41) L_(C721) R^(D133) R^(D42) L_(C722) R^(D133) R^(D43) L_(C723) R^(D133) R^(D48) L_(C724) R^(D133) R^(D49) L_(C725) R^(D133) R^(D54) L_(C726) R^(D133) R^(D58) L_(C727) R^(D133) R^(D59) L_(C728) R^(D133) R^(D78) L_(C729) R^(D133) R^(D79) L_(C730) R^(D133) R^(D81) L_(C731) R^(D133) R^(D87) L_(C732) R^(D133) R^(D88) L_(C733) R^(D133) R^(D89) L_(C734) R^(D133) R^(D93) L_(C735) R^(D133) R^(D117) L_(C736) R^(D133) R^(D118) L_(C737) R^(D133) R^(D119) L_(C738) R^(D133) R^(D120) L_(C739) R^(D133) R^(D133) L_(C740) R^(D133) R^(D134) L_(C741) R^(D133) R^(D135) L_(C742) R^(D133) R^(D136) L_(C743) R^(D133) R^(D146) L_(C744) R^(D133) R^(D147) L_(C745) R^(D133) R^(D149) L_(C746) R^(D133) R^(D151) L_(C747) R^(D133) R^(D154) L_(C748) R^(D133) R^(D155) L_(C749) R^(D133) R^(D161) L_(C750) R^(D133) R^(D175) L_(C751) R^(D175) R^(D3) L_(C752) R^(D175) R^(D5) L_(C753) R^(D175) R^(D18) L_(C754) R^(D175) R^(D20) L_(C755) R^(D175) R^(D22) L_(C756) R^(D175) R^(D37) L_(C757) R^(D175) R^(D40) L_(C758) R^(D175) R^(D41) L_(C759) R^(D175) R^(D42) L_(C760) R^(D175) R^(D43) L_(C761) R^(D175) R^(D48) L_(C762) R^(D175) R^(D49) L_(C763) R^(D175) R^(D54) L_(C764) R^(D175) R^(D58) L_(C765) R^(D175) R^(D59) L_(C766) R^(D175) R^(D78) L_(C767) R^(D175) R^(D79) L_(C768) R^(D175) R^(D81) where R^(D1) to R¹⁹² have the following structures:

In some embodiments of the compound, the ligands L_(Cj-I) and L_(Cj-II) consist of only those ligands whose corresponding R¹ and R² are defined to be selected from the following structures: R^(D1), R^(D3), R^(D4), R^(D5), R^(D9), R^(D10), R^(D17), R^(D18), R^(D20), R^(D22), R^(D3)7, R^(D40), R^(D41), R^(D42), R^(D43), R^(D48), R^(D49), R^(D50), R^(D54), R^(D55), R^(D58), R^(D59), R^(D78), R^(D79), R^(D81), R^(D87), R^(D88), R^(D89), R^(D93), R^(D116), R^(D117), R^(D118), R^(D19), R^(D120), R^(D133), R^(D134), R^(D135), R^(D136), R^(D143), R^(D144), R^(D145), R^(D146), R^(D147), R^(D149), R^(D151), R^(D154), R^(D155), R^(D161), R^(D175), and R^(D90).

In some embodiments of the compound, the ligands L_(Cj-1) and L_(Cj-II) consist of only those ligands whose corresponding R¹ and R² are defined to be selected from the following structures: R^(D1), R^(D3), R^(D4), R^(D5), R^(D9), R^(D17), R^(D22), R^(D43), R^(D50), R^(D78), R^(D116), R^(D118), R^(D133), R^(D134), R^(D135), R^(D136), R^(D143), R^(D144), R^(D145), R^(D146), R^(D149), R^(D151), R^(D154), R^(D155), and R^(D190).

In some embodiments of the compound, the ligand L_(C) is selected from the group consisting of:

In some embodiments of the compound whose ligand L_(X) has the structure of Formula IV, the first ligand L_(X) is selected from the group consisting of L_(X1-1) to L_(X897-38) with the general numbering formula L_(Xh-m), and L_(X1-39) to L_(X1446-57) with the general numbering formula L_(Xi-n); where h is an integer from 1 to 897, i is an integer from 1 to 1446, m is an integer from 1 to 38 referring to Structure 1 to Structure 38, and n is an integer from 39 to 57 referring to Structure 39 to Structure 57, the compound can be selected from the group consisting of Ir(L_(X1-1))₃ to Ir(L_(X897-38))₃ with the general numbering formula Ir(L_(Xh-m))₃, Ir(L_(X1-39))₃ to Ir(L_(X1446-57))₃ with the general numbering formula Ir(L_(Xi-n))₃, Ir(L_(X1-1))(L_(B1))₂ to Ir(L_(X897-38))(L_(B263))₂ with the general numbering formula Ir(L_(Xh-m))(L_(Bk))₂, Ir(L_(X1-39))(L_(B1))₂ to Ir(L_(X1446-57))(L_(B263))₂ with the general numbering formula Ir(L_(Xi-n))(L_(Bk))₂; where k is an integer from 1 to 263; where L_(Bk) has the structures L_(B1) to L_(B263) defined herein.

In some embodiments of the compound, the compound is selected from the group consisting of:

C. The OLEDs and the Devices of the Present Disclosure

In another aspect, the present disclosure also provides an OLED device comprising a first organic layer that contains a compound as disclosed in the above compounds section of the present disclosure.

In some embodiments, the first organic layer can comprise a compound comprising a first ligand L_(X) of Formula II

where, F is a 5-membered or 6-membered carbocyclic or heterocyclic ring; each R^(F) and R^(G) independently represents mono to the maximum possible number of substitutions, or no substitution; Z³ and Z⁴ are each independently C or N and coordinated to a metal M to form a 5-membered chelate ring; G is a fused ring structure comprising five or more fused heterocyclic or carbocyclic rings, of which at least one ring is of Formula III

the fused heterocyclic or carbocyclic rings in the fused ring structure G are 5-membered or 6-membered; of which if two or more 5-membered rings are present, at least two of the 5-membered rings are fused to one another; Y is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″; each R′, R″, R^(F), and R^(G) is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; the metal M can be coordinated to other ligands; and the ligand L_(X) can be linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand.

In some embodiments, the organic layer may be an emissive layer and the compound as described herein may be an emissive dopant or a non-emissive dopant.

In some embodiments, the organic layer may further comprise a host, wherein the host comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan, wherein any substituent in the host is an unfused substituent independently selected from the group consisting of C_(n)H_(2n+1), OC_(n)H_(2n+1), OAr₁, N(C_(n)H_(2n+1))₂, N(Ar₁)(Ar₂), CH═CH—C_(n)H_(2n+1), C≡CC_(n)H_(2n+1), Ar₁, Ar₁—Ar₂, C_(n)H_(2n)—Ar₁, or no substitution, wherein n is from 1 to 10; and wherein Ar₁ and Ar₂ are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.

In some embodiments, the organic layer may further comprise a host, wherein host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

In some embodiments, the host may be selected from the group consisting of:

and combinations thereof.

In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.

In some embodiments, the compound as described herein may be a sensitizer; wherein the device may further comprise an acceptor; and wherein the acceptor may be selected from the group consisting of fluorescent emitter, delayed fluorescence emitter, and combination thereof.

In yet another aspect, the OLED of the present disclosure may also comprise an emissive region containing a compound as disclosed in the above compounds section of the present disclosure.

In some embodiments, the emissive region can comprise a compound comprising a first ligand L_(X) of Formula II

where, F is a 5-membered or 6-membered carbocyclic or heterocyclic ring; each R^(F) and R^(G) independently represents mono to the maximum possible number of substitutions, or no substitution; Z³ and Z⁴ are each independently C or N and coordinated to a metal M to form a 5-membered chelate ring; G is a fused ring structure comprising five or more fused heterocyclic or carbocyclic rings, of which at least one ring is of Formula III

the fused heterocyclic or carbocyclic rings in the fused ring structure G are 5-membered or 6-membered; of which if two or more 5-membered rings are present, at least two of the 5-membered rings are fused to one another; Y is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″; each R′, R″, R^(F), and R^(G) is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; the metal M can be coordinated to other ligands; and the ligand L_(X) can be linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand.

In some embodiments of the emissive region, the compound can be an emissive dopant or a non-emissive dopant. In some embodiments of the emissive region, the emissive region further comprises a host, where the host contains at least one group selected from the group consisting of metal complex, triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, aza-triphenylene, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. In some embodiments of the emissive region, the emissive region further comprises a host, where the host is selected from the Host Group defined above.

In yet another aspect, the present disclosure also provides a consumer product comprising an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound as disclosed in the above compounds section of the present disclosure.

In some embodiments, the consumer product comprises an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer can comprise a compound comprising a first ligand L_(X) of Formula

where, F is a 5-membered or 6-membered carbocyclic or heterocyclic ring; each R and Ru independently represents mono to the maximum possible number of substitutions, or no substitution; Z³ and Z⁴ are each independently C or N and coordinated to a metal M to form a 5-membered chelate ring; G is a fused ring structure comprising five or more fused heterocyclic or carbocyclic rings, of which at least one ring is of Formula III

the fused heterocyclic or carbocyclic rings in the fused ring structure G are 5-membered or 6-membered; of which if two or more 5-membered rings are present, at least two of the 5-membered rings are fused to one another; Y is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″; each R′, R″, R^(F), and R^(G) is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; the metal M can be coordinated to other ligands; and the ligand L_(X) can be linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand.

In some embodiments, the consumer product can be one of a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device, and a sign.

Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.

Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.

More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.

FIG. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference.

More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F₄-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an “inverted” OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides one example of how some layers may be omitted from the structure of device 100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the present disclosure may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to FIGS. 1 and 2.

Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.

Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and organic vapor jet printing (OVJP). Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons are a preferred range. Materials with asymmetric structures may have better solution processability than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

Devices fabricated in accordance with embodiments of the present disclosure may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.

Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. A consumer product comprising an OLED that includes the compound of the present disclosure in the organic layer in the OLED is disclosed. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro-displays (displays that are less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screen, a light therapy device, and a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present disclosure, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25° C.), but could be used outside this temperature range, for example, from −40 degree C. to +80° C.

More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.

The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.

In some embodiments, the OLED has one or more characteristics selected from the group consisting of being flexible, being rollable, being foldable, being stretchable, and being curved. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.

In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises a RGB pixel arrangement or white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a hand held device, or a wearable device. In some embodiments, the OLED is a display panel having less than 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a display panel having at least 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a lighting panel.

In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence; see, e.g., U.S. application Ser. No. 15/700,352, which is hereby incorporated by reference in its entirety), triplet-triplet annihilation, or combinations of these processes. In some embodiments, the emissive dopant can be a racemic mixture, or can be enriched in one enantiomer. In some embodiments, the compound can be homoleptic (each ligand is the same). In some embodiments, the compound can be heteroleptic (at least one ligand is different from others). When there are more than one ligand coordinated to a metal, the ligands can all be the same in some embodiments. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, every ligand can be different from each other. This is also true in embodiments where a ligand being coordinated to a metal can be linked with other ligands being coordinated to that metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligands. Thus, where the coordinating ligands are being linked together, all of the ligands can be the same in some embodiments, and at least one of the ligands being linked can be different from the other ligand(s) in some other embodiments.

In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED where one or multiple layers in the OLED contains an acceptor in the form of one or more fluorescent and/or delayed fluorescence emitters. In some embodiments, the compound can be used as one component of an exciplex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be capable of energy transfer to the acceptor and the acceptor will emit the energy or further transfer energy to a final emitter. The acceptor concentrations can range from 0.001% to 100%. The acceptor could be in either the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission can arise from any or all of the sensitizer, acceptor, and final emitter.

According to another aspect, a formulation comprising the compound described herein is also disclosed.

The OLED disclosed herein can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel. The organic layer can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.

In yet another aspect of the present disclosure, a formulation that comprises the novel compound disclosed herein is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, electron blocking material, hole blocking material, and an electron transport material, disclosed herein.

The present disclosure encompasses any chemical structure comprising the novel compound of the present disclosure, or a monovalent or polyvalent variant thereof. In other words, the inventive compound, or a monovalent or polyvalent variant thereof, can be a part of a larger chemical structure. Such chemical structure can be selected from the group consisting of a monomer, a polymer, a macromolecule, and a supramolecule (also known as supermolecule). As used herein, a “monovalent variant of a compound” refers to a moiety that is identical to the compound except that one hydrogen has been removed and replaced with a bond to the rest of the chemical structure. As used herein, a “polyvalent variant of a compound” refers to a moiety that is identical to the compound except that more than one hydrogen has been removed and replaced with a bond or bonds to the rest of the chemical structure. In the instance of a supramolecule, the inventive compound can also be incorporated into the supramolecule complex without covalent bonds.

D. Combination of the Compounds of the Present Disclosure with Other Materials

The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.

a) Conductivity Dopants:

A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer.

Non-limiting examples of the conductivity dopants that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.

b) HIL/HTL:

A hole injecting/transporting material to be used in the present disclosure is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoO_(x); a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.

Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:

Each of Ar¹ to Ar⁹ is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each Ar may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, Ar¹ to Ar⁹ is independently selected from the group consisting of:

wherein k is an integer from 1 to 20; X¹⁰¹ to X¹⁰⁸ is C (including CH) or N; Z¹⁰¹ is NAr¹, O, or S; Ar¹ has the same group defined above.

Examples of metal complexes used in HIL or HTL include, but are not limited to the following general formula:

wherein Met is a metal, which can have an atomic weight greater than 40; (Y¹⁰¹-Y¹⁰²⁾ is a bidentate ligand, Y¹⁰ and Y^(1O2) are independently selected from C, N, O, P, and S; L¹⁰¹ is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.

In one aspect, (Y¹⁰¹-Y^(1O2)) is a 2-phenylpyridine derivative. In another aspect, (Y¹⁰¹-Y¹⁰²) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc⁺/Fc couple less than about 0.6 V.

Non-limiting examples of the HIL and HTL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, U.S. Pat. No. 6,517,957, US20020158242, US20030162053, US20050123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US2011007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, U.S. Pat. Nos. 5,061,569, 5,639,914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO2013087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018.

c) EBL:

An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and/or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.

d) Hosts:

The light emitting layer of the organic EL device of the present disclosure preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria is satisfied.

Examples of metal complexes used as host are preferred to have the following general formula:

wherein Met is a metal; (Y¹⁰³-Y¹⁰⁴) is a bidentate ligand, Y¹⁰³ and Y¹⁰⁴ are independently selected from C, N, O, P, and S; L¹⁰¹ is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.

In one aspect, the metal complexes are:

wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.

In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y¹⁰³-Y¹⁰⁴) is a carbene ligand.

In one aspect, the host compound contains at least one of the following groups selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each option within each group may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, the host compound contains at least one of the following groups in the molecule:

wherein R¹⁰¹ is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. k is an integer from 0 to 20 or 1 to 20. X¹⁰¹ to X^(08s) are independently selected from C (including CH) or N. Z¹⁰¹ and Z¹⁰² are independently selected from NR¹⁰¹, O, or S.

Non-limiting examples of the host materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, U.S. Pat. No. 7,154,114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, U.S. Pat. No. 9,466,803,

e) Additional Emitters:

One or more additional emitter dopants may be used in conjunction with the compound of the present disclosure. Examples of the additional emitter dopants are not particularly limited, and any compounds may be used as long as the compounds are typically used as emitter materials. Examples of suitable emitter materials include, but are not limited to, compounds which can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.

Non-limiting examples of the emitter materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, U.S. Ser. No. 06/699,599, U.S. Ser. No. 06/916,554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670, US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, US20080233410, US20080261076, US20080297033, US200805851, US2008161567, US2008210930, US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663, US20100244004, US20100295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559, US20110108822, US20110204333, US2011215710, US2011227049, US2011285275, US2012292601, US20130146848, US2013033172, US2013165653, US2013181190, US2013334521, US20140246656, US2014103305, U.S. Pat. Nos. 6,303,238, 6,413,656, 6,653,654, 6,670,645, 6,687,266, 6,835,469, 6,921,915, 7,279,704, 7,332,232, 7,378,162, 7,534,505, 7,675,228, 7,728,137, 7,740,957, 7,759,489, 7,951,947, 8,067,099, 8,592,586, 8,871,361, WO06081973, WO06121811, WO07018067, WO007108362, WO07115970, WO07115981, WO08035571, WO2002015645, WO2003040257, WO2005019373, WO2006056418, WO2008054584, WO2008078800, WO2008096609, WO2008101842, WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO2011044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO2013174471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450.

f) HBL:

A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.

In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.

In another aspect, compound used in HBL contains at least one of the following groups in the molecule:

wherein k is an integer from 1 to 20; L¹⁰¹ is another ligand, k′ is an integer from 1 to 3.

g) ETL:

Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.

In one aspect, compound used in ETL contains at least one of the following groups in the molecule:

wherein R¹⁰¹ is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. Ar¹ to Ar³ has the similar definition as Ar's mentioned above. k is an integer from 1 to 20. X¹⁰¹ to X¹⁰⁸ is selected from C (including CH) or N.

In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:

wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L¹⁰¹ is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.

Non-limiting examples of the ETL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, U.S. Pat. Nos. 6,656,612, 8,415,031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,

h) Charge Generation Layer (CGL)

In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers.

In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. may be undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also may be undeuterated, partially deuterated, and fully deuterated versions thereof.

It is understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.

EXPERIMENTAL Synthesis of IrL_(X584-17)(L_(B118))₂

Phenanthren-9-ol (16 g, 82 mmol) was dissolved in 100 mL of dimethylformamide (DMF) and was cooled in an ice bath. 1-Bromopyrrolidine-2,5-dione (NBS, 14.95 g, 84 mmol) was dissolved in 50 mL of DMF and was added dropwise to the cooled reaction mixture over a 15-minute period. Stirring was continued for 30 minutes, then reaction was quenched with 300 mL of water. This mixture was extracted by dichloromethane (DCM). The DCM extracts were washed with aqueous LiCl then were dried over magnesium sulfate. These extracts were then filtered and concentrated under vacuum. The crude residue was passed through silica gel column eluting with 20-23% DCM in heptanes. Pure product fractions were combined and concentrated in vacuo to afford 10-bromophenanthren-9-ol (12.07 g, 44.2 mmol, 53.6% yield).

10-bromophenanthren-9-ol (13.97 g, 51.1 mmol) was charged into the reaction flask with 100 mL of dry DMF. This solution was cooled in a wet ice bath followed by the portion wise addition of sodium hydride (2.97 g, 74.2 mmol) over a 15 minute period. This mixture was then stirred for 1 hour and cooled using a wet ice bath. Iodomethane (18.15 g, 128 mmol) was dissolved in 70 mL of DMF, then was added dropwise to the cooled reaction mixture. This mixture developed a thick tan precipitate. Stirring was continued as the mixture gradually warmed up to room temperature (˜22° C.). The reaction mixture was quenched with 300 mL of water then extracted with DCM. The organic extracts were combined, washed with aqueous LiCl then dried over magnesium sulfate. These extracts were filtered and concentrated in vacuo. The crude residue was passed through silica gel column eluting with 15-22% DCM in heptanes. Pure product fractions yielded 9-bromo-10-methoxyphenanthrene (5.72 g, 19.92 mmol, 38.9% yield) as a light yellow solid.

9-bromo-10-methoxyphenanthrene (8.75 g, 30.5 mmol), (3-chloro-2-fluorophenyl)boronic acid (6.11 g, 35.0 mmol), potassium phosphate tribasic monohydrate (21.03 g, 91 mmol), tris(dibenzylideneacetone)palladium(0) (Pd₂(dba)₃)(0.558 g, 0.609 mmol) and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (Sphos) (1.4 g, 3.41 mmol) were suspended in 300 mL of toluene. This mixture was degassed with nitrogen then heated to reflux for 18 hours. Heating was discontinued and the reaction mixture was diluted with 300 mL of water. The toluene layer was separated and was dried over magnesium sulfate. The organic solution was filtered and concentrated in vacuo. The crude residue was passed through silica gel columns eluting the columns with 25-30% DCM in heptanes. Pure product fractions were combined and concentrated yielding 9-(3-chloro-2-fluorophenyl)-10-methoxyphenanthrene (8.75 g, 260 mmol, 85% yield) as a white solid.

9-(3-chloro-2-fluorophenyl)-10-methoxyphenanthrene (1.5 g, 4.45 mmol) was dissolved in 40 mL of DCM. This homogeneous mixture was cooled to 0° C. A 1M boron tribromide (BBr₃) solution in DCM (11.13 ml, 11.13 mmol) was added dropwise to the reaction mixture over a 5-minute period. Stirring was continued at 0° C. for 3.5 hours. The reaction mixture was poured into a beaker of wet ice. The organic layer was separated. The aqueous phase was extracted with DCM. The DCM extracts were combined with organic phase and washed with aqueous LiCl then dried over magnesium sulfate. This solution was filtered and concentrated in vacuo yielding 10-(3-chloro-2-fluorophenyl)phenanthren-9-ol (1.4 g, 4.34 mmol, 97% yield) as an off-white solid.

3-Chloro-10-(2-fluorophenyl)phenanthren-9-ol (1.4 g, 4.34 mmol) and potassium carbonate (1.796 g, 13.01 mmol) were suspended in 1-methylpyrrolidin-2-one (15 ml, 156 mmol). This mixture was degassed with nitrogen then was heated in an oil bath set at 150° C. for 18 h. The reaction mixture was cooled down to room temperature, diluted with 200 mL of water, and grey precipitate was filtered under reduced pressure. This solid was dissolved in hot DCM, washed with aqueous LiCl, then dried over magnesium sulfate. The solution was filtered and concentrated in vacuo yielding 10-chlorophenanthro[9,10-b]benzofuran (1.23 g, 4.06 mmol, 94% yield).

10-Chlorophenanthro[9,10-b]benzofuran (1.23 g, 4.06 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (1.341 g, 5.28 mmol), tris(dibenzylideneacetone)palladium(0) (0.093 g, 0.102 mmol) and SPhos (0.250 g, 0.609 mmol) were suspended in 80 mL of dioxane. Potassium acetate (0.995 g, 10.16 mmol) was then added to the reaction flask as one portion. This mixture was degassed with nitrogen then heated to reflux for 18 hours. Heating was discontinued. 2-Bromo-4,5-bis(methyl-d3)pyridine (1.052 g, 5.48 mmol), tetrakis(triphenylphosphine)palladium(0) (Pd(PPh₃)₄) (0.140 g, 0.122 mmol) and potassium phosphate tribasic monohydrate (2.80 g, 12.17 mmol) were added followed by 10 mL of water. This mixture was degassed with nitrogen then was heated to reflux for 18 hours. The reaction mixture was cooled to room temperature (˜22° C.) then was diluted with 200 mL of water. This mixture was extracted with DCM, extracts were combined, washed with aqueous LiCl, then dried over magnesium sulfate. These extracts were filtered and concentrated in vacuo. The crude residue was passed through a silica gel column eluting with 0.5-4% ethyl acetate in DCM. Pure fractions were combined together and concentrated under vacuum yielding 4,5-bis(methyl-d3)-2-(phenanthro[9,10-b]benzofuran-10-yl)pyridine 1.13 g, 2.98 mmol, 73.4% yield).

4,5-bis(Methyl-d3)-2-(phenanthro[9,10-b]benzofuran-10-yl)pyridine (2 g, 5.27 mmol) and the iridium complex triflic salt shown above (2.445 g, 2.85 mmol) were suspended in the mixture of 25 mL of 2-ethoxyethanol and 25 mL of DMF. This mixture was degassed with nitrogen, then heated at 95° C. for 21 days. The reaction mixture was cooled down and diluted with 150 mL of methanol. A yellow precipitate was collected and dried in vacuo. This solid was then dissolved in 500 mL of DCM and was passed through a plug of basic alumina. The DCM filtrate was concentrated and dried in vacuo leaving an orange colored solid. This solid was passed through a silica gel column eluting with 10% DCM/45% toluene/heptanes and then 65% toluene in heptanes.

Pure fractions after evaporation yielded the desired iridium complex, IrL_(X36)(L_(B461))₂ (1.07 g, 1.046 mmol, 36.7% yield).

Synthesis of IrL_(X588-12)(L_(B118))₂

(4-Methoxyphenyl)boronic acid (22.50 g, 148 mmol) and potassium phosphate tribasic monohydrate (68.2 g, 296 mmol) were suspended in 500 mL of toluene and 10 mL of water. The reaction mixture was purged with nitrogen for 15 min then tris(dibenzylideneacetone)dipalladium(0) (2.71 g, 2.96 mmol), dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphane (Sphos, 4.86 g, 11.85 mmol) and ((2-bromophenyl)ethynyl)trimethylsilane (35.3 ml, 99 mmol) were added. The reaction mixture was heated in an oil bath set at 100° C. for 13 hours under nitrogen. The reaction mixture was filtered through silica gel and the filtrate was concentrated down to a brown oil. The brown oil was purified on a silica gel column eluting with heptane/DCM 75/25 (v/v) mixture to get ((4′-methoxy-[1,1′-biphenyl]-2-yl)ethynyl)trimethylsilane (25.25 g, 91% yield).

((4′-Methoxy-[1,1′-biphenyl]-2-yl)ethynyl)trimethylsilane (25.2 g, 90 mmol) was dissolved in 300 mL of tetrahydrofuran (THF). The reaction was cooled in an ice bath then a 1 M solution of tetra-n-butylammonium fluoride in THF (108 mL, 108 mmol) was added dropwise. The reaction mixture was allowed to warm up to room temperature. After two hours the reaction mixture was concentrated down, washed with ammonium chloride solution and brine, dried over sodium sulfate, filtered and concentrated down to a brown oil. The brown oil was purified on a silica gel column eluting with heptane/DCM 75/25 (v/v) to produce 2-ethynyl-4′-methoxy-1,1′-biphenyl as an orange oil (17.1 g, 91% yield).

2-Ethynyl-4′-methoxy-1,1′-biphenyl (19.5 g, 94 mmol) was dissolved in 600 ml of toluene and platinum(II) chloride (2.490 g, 9.36 mmol) was added as a slurry mixture in 200 ml of toluene. The reaction was heated to 80° C. for 14 hours. The reaction was then cooled down and filtered through a silica gel plug. The filtrate was concentrated down to a brown solid. The solid was purified on a silica gel column eluting with heptane/DCM 75/25 (v/v) to afford 2-methoxyphenanthrene as off-white solid (14.0 g, 71.8% yield).

2-Methoxyphenanthrene (11.7 g, 56.2 mmol) was dissolved in dry THF (300 ml) under nitrogen. The solution was cooled in a brine/dry ice bath to maintain a temperature below −10° C., then a sec-butyllithium THF solution (40.4 ml, 101 mmol) was added in portions keeping the temperature of the mixture below −10° C. The reaction mixture immediately turned dark. The reaction mixture was continuously stirred in the cooling bath for 1 hour. Then the reaction mixture was removed from the bath and stirred at room temperature for three hours.

The reaction was placed back in the cooling bath for 30 min, then 1,2-dibromoethane (11.14 ml, 129 mmol) was added in portions keeping the temperature below −10° C. The reaction was allowed to warm up room temperature over 16 hours. The reaction mixture was then diluted with water and extracted with ethyl acetate. The combined organic extracts were washed with saturated brine once, then dried over sodium sulfate, filtered, and concentrated down to a brown solid. The solid was purified on a silica gel column, eluted with heptane/DCM 75/25 (v/v) to provide 3-bromo-2-methoxyphenanthrene as a white solid (13.0 g, 80% yield).

3-Bromo-2-methoxyphenanthrene (13.0 g, 45.3 mmol), (3-chloro-2-fluorophenyl)boronic acid (7.89 g, 45.3 mmol), potassium phosphate tribasic monohydrate (31.3 g, 136 mmol) and toluene (400 ml) were combined in a flask. The solution was purged with nitrogen for 15 min, then tris(dibenzylideneacetone)dipalladium(0) (1.244 g, 1.358 mmol) and dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphane (SPhos, 2.230 g, 5.43 mmol) were added. The reaction mixture was heated to reflux under nitrogen for 13 hours. Another 0.5 g of (3-chloro-2-fluorophenyl)boronic acid, 0.2 g of Pd₂dba₃ and 0.4 g of dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphane were added and the reaction mixture was maintained at reflux for another day to complete the reaction.

The resulting reaction solution was decanted off and the flask was rinsed twice with ethyl acetate. The resulting black residue was dissolved with water, extracted twice with ethyl acetate, and then filtered through filter paper to remove the black precipitate. The combined organic solution was washed once with brine, dried over sodium sulfate, filtered and concentrated down to a brown solid. The brown solid was purified on a silica gel column, eluting with heptanes/DCM 75/25 (v/v) mixture to isolate 3-(3-chloro-2-fluorophenyl)-2-methoxyphenanthrene (6.95 g, 45.6% yield).

3-(3-Chloro-2-fluorophenyl)-2-methoxyphenanthrene (6.9 g, 20.49 mmol) was dissolved in DCM (100 mL) and was cooled in a brine/ice bath. Boron tribromide 1 M solution in DCM (41.0 mL, 41.0 mmol) was added rapidly dropwise, then the reaction was allowed to warm up to room temperature (˜22° C.) and stirred for 4 hours. The reaction was cooled in an ice bath, then carefully quenched with cold water. The reaction was stirred for 30 minutes, then more water was added and reaction was extracted with DCM. The combined DCM solution was washed once with water, dried over sodium sulfate, filtered and concentrated down to isolate 3-(3-chloro-2-fluorophenyl)phenanthren-2-ol as a beige solid (6.55 g, 99% yield).

3-(3-Chloro-2-fluorophenyl)phenanthren-2-ol (6.5 g, 20.14 mmol) was dissolved in 1-methylpyrrolidin-2-one (NMP) (97 ml, 1007 mmol). The reaction was purged with nitrogen for 15 min, then potassium carbonate (8.35 g, 60.4 mmol) was added. The reaction was heated under nitrogen in an oil bath set at 150° C. for 8 hours. The reaction was diluted with water and extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over sodium sulfate, filtered and concentrated down to a beige solid. The beige solid was purified on a silica gel column eluted with heptanes/DCM 85/15 (v/v) to obtain 9-chlorophenanthro[2,3-b]benzofuran as a white solid (5.5 g, 91% yield).

9-Chlorophenanthro[2,3-b]benzofuran (5.2 g, 17.18 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (8.72 g, 34.4 mmol), and potassium acetate (5.06 g, 51.5 mmol) were suspended in 1,4-dioxane (150 ml). The reaction mixture was purged with nitrogen for 15 min, then tris(dibenzylideneacetone)dipalladium(0) (0.315 g, 0.344 mmol) and dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphane (SPhos, 0.564 g, 1.374 mmol) were added. The reaction was heated in an oil bath set at 110° C. for 14 hours. The reaction was cooled to room temperature, then 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine (3.48 g, 17.18 mmol), potassium phosphate tribasic hydrate (10.94 g, 51.5 mmol) and 40 ml water were added. The reaction was purged with nitrogen for 15 min then tetrakis(triphenylphosphine)palladium(0) (0.595 g, 0.515 mmol) was added. The reaction was heated in an oil bath set at 100° C. for 14 hours.

The reaction mixture was diluted with ethyl acetate, washed once with water then brine once, then dried over sodium sulfate, filtered, then concentrated down to a beige solid. The beige solid was purified on a silica gel column eluting with heptanes/ethyl acetate/DCM 80/10/10 to 75/10/15 (v/v/v) gradient mixture to get 4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)-2-(phenanthro[2,3-b]benzofuran-9-yl)pyridine (5.9 g, light yellow solid). The sample was additionally purified on a silica gel column eluting with toluene/ethyl acetate/DCM 85/5/10 to 75/10/15 (v/v/v) gradient mixture, providing 4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)-2-(phenanthro[2,3-b]benzofuran-9-yl)pyridine as a white solid (3.75 g, 50.2% yield).

The triflic salt complex of iridium shown above (2.1 g, 2.61 mmol) and 4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)-2-(phenanthro[2,3-b]benzofuran-9-yl)pyridine (2.043 g, 4.70 mmol) were suspended in DMF (30 ml) and 2-ethoxyethanol (30.0 ml) mixture. The reaction mixture was purged with nitrogen for 15 min then heated to 80° C. for 10 days. The solvents were evaporated in vacuo, and the residue then was diluted with methanol (MeOH). A brown-yellow precipitate was filtered off and washed with MeOH. The precipitate was purified on a silica gel column eluting with heptanes/toluene 25/75 to 10/90 (v/v) gradient mixture to get a yellow solid. The solid was dissolved in DCM, the ethyl acetate was added and the resulting mixture concentrated down on the rotovap. The precipitate was filtered off and dried for 4 hours in vacuo to obtain the target compound, IrL_(X69)(L_(B46)1)₂, as a bright yellow solid (1.77 g, 62.8% yield).

Synthesis of IrL_(X584-11)(L_(B118))₂

Dibenzo[b,d]furan (38.2 g, 227 mmol) was dissolved in dry THF (450 ml) under a nitrogen atmosphere. The solution was cooled in a dry ice-acetone bath, then a 2.5 M n-butyllithium solution in hexanes (100 ml, 250 mmol) was added dropwise. The reaction mixture was stirred at room temperature (˜22° C.) for 5 hours, then cooled in a dry ice-acetone bath. Iodine (57.6 g, 227 mmol) in 110 mL of THF was added dropwise, then the resulting mixture was allowed to warm to room temperature over 16 hours. Saturated sodium bicarbonate solution and ethyl acetate were added and the resulting reaction mixture was stirred, the layers separated, and the aqueous phase was extracted with ethyl acetate while the combined organic extracts were washed with sodium bisulfite solution, dried over magnesium sulfate, filtered and evaporated. The resulting composition was purified on a silica gel column eluting with heptane, the recrystallized from 250 mL heptanes. The solid material was filtered off, washed with heptane and dried, to yield 4-iododibenzo[b,d]furan (43.90 g, 64% yield).

4-Iododibenzo[b,d]furan (10.52 g, 35.8 mmol), 2-bromobenzoic acid (14.38 g, 71.5 mmol), tricyclohexylphosphine tetraflouroborate (1.970 g, 5.37 mmol), and cesium carbonate (46.6 g, 143 mmol) were suspended in dioxane (300 ml). The reaction mixture was degassed and bicyclo[2.2.1]hepta-2,5-diene (14.49 ml, 143 mmol) was added followed by palladium acetate (0.402 g, 1.789 mmol). The reaction mixture was then heated to 130° C. After 2 hours, bicyclo[2.2.1]hepta-2,5-diene (14.49 ml, 143 mmol) at 130° C. for 16 hours under nitrogen. Water was added and the resulting composition was extracted twice with ethyl acetate. The organic solution was dried over magnesium sulfate, filtered, evaporated, and the residue dissolved in DCM. The target compound was purified using a silica gel column eluting with 0-40% DCM in heptanes. The resulting product was then triturated with heptanes, filtered, and washed with heptanes to yield phenanthro[1,2-b]benzofuran (5.0 g, 52% yield).

Phenanthro[1,2-b]benzofuran (4 g, 14.91 mmol) was dissolved in dry THF (80 mL). The solution was cooled in a dry ice-acetone bath, and sec-butyllithium hexanes solution (15.97 ml, 22.36 mmol) was added. The reaction was stirred in a cooling bath for 3 hours, and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6.08 ml, 29.8 mmol) in 10 mL THF was added and the resulting reaction mixture was stirred for 16 hours at room temperature under nitrogen. The resulting mixture was quenched with water, extracted twice with ethyl acetate, then the organics were washed with brine, dried organics over magnesium sulfate, filtered, evaporated to yield 4,4,5,5-Tetramethyl-2-(phenanthro[1,2-b]benzofuran-12-yl)-1,3,2-dioxaborolane (5.88 g) as a solid.

4,4,5,5-Tetramethyl-2-(phenanthro[1,2-b]benzofuran-12-yl)-1,3,2-dioxaborolane (7.3 g, 17.59 mmol), 2-bromo-4,5-bis(methyl-d3)pyridine (3.72 g, 19.35 mmol), dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphane (SPhos, 0.433 g, 1.055 mmol), and potassium phosphate tribasic monohydrate (8.10 g, 35.2 mmol) were suspended in a dimethyl ether (DME)(120 mL) and water (20.00 mL) mixture. The reaction mixture was degassed, tris(dibenzylideneacetone)dipalladium(0) (0.483 g, 0.528 mmol) was added, and the resulting mixture heated to 100° C. under nitrogen for 13 hours. The mixture was then diluted with water and ethyl acetate, and an insoluble solid was filtered off, the layers separated with the aqueous layer being extracted with ethyl acetate and the organics being dried over magnesium sulfate. They were then filtered and evaporated to a brown oil. Very little product in the brown oil. The insoluble material is the product. Most of the insoluble material was dissolved in 350 mL of hot DCM, filtered through a silica plug to remove a black impurity and a small amount of insoluble white solid. A white solid precipitated out of the yellow filtrate. The solid was filtered off to obtain 4,5-bis(methyl-d3)-2-(phenanthro[1,2-b]benzofuran-12-yl)pyridine as white solid (2.27 g, 34% yield).

4,5-Bis(methyl-d3)-2-(phenanthro[1,2-b]benzofuran-12-yl)pyridine (2.70 g, 7.13 mmol) was suspended in DMF (120 ml), heated to 100° C. in an oil bath to dissolve solid materials. 2-ethoxyethanol (40 ml) was added, then the resulting mixture was cooled until a solid precipitated and the iridium complex triflic salt (3.38 g, 4.07 mmol) shown above degassed and heated to 100° C. under nitrogen until the solids dissolved. The resulting mixture was heated at 100° C. under nitrogen for 2 weeks before being cooled down to room temperature. The solvent was then evaporated in vacuo. The solid residue was purified by column chromatography on a silica gel column, eluting with 70 to 90% toluene in heptanes. The target material, IrL_(X99)(L_(B461))₂, was isolated as a bright yellow solid (1.53 g, 37% yield).

Synthesis of Compound IrL_(X588-11)(L_(B132))₂

Compound IrL_(X588-11)(L_(B132))₂ was synthesized using the same techniques as IrL_(X588-11)(L_(B118))₂.

Synthesis of IrL_(X588-35)(L_(B118))₂

(4-Methoxyphenyl)boronic acid (26.2 g, 173 mmol) and potassium carbonate (47.7 g, 345 mmol) were suspended in DME (500 ml) and water (125 ml). The solution was purged with nitrogen for 15 min then 1-bromo-2-ethynylbenzene (25 g, 138 mmol) and tetrakis(triphenylphosphine) palladium(0) (4.79 g, 4.14 mmol) were added. The reaction mixture was heated to reflux under nitrogen for 14 hours. The heating was stopped, and the organic phase was separated and concentrated down to a dark oil. It was purified by column chromatography on silica gel, eluted with heptanes/DCM 3/1 (v/v), providing 2-ethynyl-4′-methoxy-1,1′-biphenyl as an orange oil (20.0 g, 69% yield).

2-Ethynyl-4′-methoxy-1,1′-biphenyl (20 g, 96 mmol) and platinum(II) chloride (2.55 g, 9.60 mmol) were suspended in 600 ml of toluene. The reaction was heated to 80° C. for 14 hours. Toluene was evaporated, and the residue was subjected to column chromatography on a silica gel eluted with heptanes/DCM 85/15 (v/v) to isolate 2-methoxyphenanthrene (13.8 g, 69% yield).

2-Methoxyphenanthrene (13.86 g, 66.6 mmol) was dissolved in acetonitrile (500 ml) and the mixture was cooled to −20° C. Trifluoromethanesulfonic acid (6.46 ml, 73.2 mmol) was slowly added, followed by 1-bromopyrrolidine-2,5-dione (13.03 g, 73.2 mmol). The mixture was allowed to warm up to room temperature and stirred for 5 hours. The reaction was quenched with water and extracted with ethyl acetate (EtOAc). The organic extracts were combined, dried over sodium sulfate, filtered and evaporated. The residue was purified on silica gel column eluted with 20% DCM in heptane to isolate 1-bromo-2-methoxyphenanthrene (21 g, 99% yield).

1-Bromo-2-methoxyphenanthrene (19 g, 66.2 mmol), tris(dibenzylideneacetone)dipalladium(0) (1.212 g, 1.323 mmol), (3-chloro-2-fluorophenyl)boronic acid (13.84 g, 79 mmol), SPhos (2.173 g, 5.29 mmol) and potassium phosphate tribasic monohydrate (3 eq.) were suspended in DME (250 ml)/water (50.0 ml). The mixture was degassed and heated to 90° C. for 14 hours. After the reaction mixture was cooled down to room temperature, the mixture was diluted with water and extracted with ethyl acetate (EtOAc). The organic phase was separated, dried over sodium sulfate, filtered and evaporated. The resulting residue was purified on a silica gel column eluted with a mixture of heptane and DCM (8/2, v/v) to give yield 1-(3-chloro-2-fluorophenyl)-2-methoxyphenanthrene (19 g, 56.4 mmol, 85% yield).

1-(3-Chloro-2-fluorophenyl)-2-methoxyphenanthrene (19 g, 56.4 mmol) was dissolved in DCM (200 ml) and cooled in the ice bath. A 1 M boron tribromide solution in DCM (113 ml, 113 mmol) was added dropwise. The mixture was stirred at room temperature for 16 hours and quenched with water at 0° C. The mixture was extracted with DCM, and the organic phases were combined. The solvent was evaporated, and the residue was purified on a silica gel column eluted with 7/3 DCM/heptane (v/v) to yield 1-(3-chloro-2-fluorophenyl)phenanthren-2-ol (16.5 g, 51.1 mmol, 91% yield).

A mixture of 1-(3-chloro-2-fluorophenyl)phenanthren-2-ol (16.5 g, 51.1 mmol) and K₂CO₃ (21.20 g, 153 mmol) in 1-methylpyrrolidin-2-one (271 ml, 2812 mmol) was vacuumed and filled with argon gas. The mixture was heated at 150° C. for 16 hours. After cooling to room temperature, the solution was extracted with EtOAc, and the organic extract was washed with brine. The solvent was evaporated, and the residue was purified on a silica gel column eluted with a heptane/DCM gradient mixture followed by crystallization from DCM/heptanes to give 8-chlorophenanthro[2,1-b]benzofuran (10 g, 33.0 mmol, 64.6% yield).

8-Chlorophenanthro[2,1-b]benzofuran (3.0 g, 9.91 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (5.03 g, 19.8 mmol) and potassium acetate (2.92 g, 30 mmol) were suspended in 100 mL of dry 1,4-dioxane. Tris(dibenzylideneacetone)dipalladium(0) (181 mg, 2 mol. %) and dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphane (Sphos, 325 mg, 8 mol. %) were added as one portion. The reaction mixture was degassed and heated to reflux under nitrogen for 14 hours. It was then cooled down to room temperature, and sodium carbonate (3.15 g, 30 mmol), 10 mL of water, tetrakis(triphenylphosphine)palladium(0) (344 mg, 3 mol. %) and 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine (2.03 g, 9.9 mmol) were added. The reaction mixture was degassed and heated to reflux under nitrogen for 12 hours. The organic phase was separated, while the aqueous phase was extracted with ethyl acetate. The combined organic solutions were dried over sodium sulfate, filtered and evaporated. The residue was subjected to column chromatography on silica gel eluted with heptanes/ethyl acetate 5-10% gradient mixture to yield 4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)-2-(phenanthro[2,1-b]benzofuran-8-yl)pyridine as white solid (2.37 g, 63% yield).

The iridium complex triflic salt shown above (2.0 g, 2.33 mmol) and 4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)-2-(phenanthro[2,1-b]benzofuran-8-yl)pyridine (2.127 g, 4.89 mmol) were suspended in a DMF (30 mL)/2-ethoxyethanol (30 mL) mixture. The reaction mixture was degassed and heated to 100° C. for 10 days. Solvents were evaporated in vacuum, and the residue was subjected to column chromatography on silica gel column eluted with toluene/DCM/heptanes 4/3/3 (v/v/v) to produce the target material, IrL_(X512)(L_(B461))₂, as bright yellow solid (1.25 g, 50% yield).

Synthesis of IrL_(X36-5)(L_(B132))₂

In a nitrogen flushed 500 mL two-necked round-bottomed flask, 1-iodo-4-methoxybenzene (12 g, 51.3 mmol), 2-bromobenzoic acid (20.61 g, 103 mmol), cesium carbonate (75 g, 231 mmol), diacetoxypalladium (Pd(OAc)₂) (0.576 g, 2.56 mmol) and tricyclohexylphosphine, BF₄— salt (2.82 g, 7.69 mmol) were dissolved in 200 ml of 1,4-dioxane under nitrogen to give a red suspension. The reaction mixture was heated to reflux under nitrogen for 14 hours. It was then cooled down to room temperature, diluted with water and extracted with EtOAc. Organic solution was dried over Na₂SO₄ and evaporated. The crude product was added to a silica gel column and was eluted with DCM/heptanes gradient mixture to give 3-methoxyphenanthrene (3.5 g, 16.81 mmol, 32.8% yield) as a yellow solid.

3-Methoxyphenanthrene (2.73 g, 13.11 mmol) was dissolved in dry THF under a nitrogen atmosphere and cooled in an IPA/dry ice bath. A solution of n-butyllithium in THF (8.39 ml, 20.97 mmol) was added to the reaction via syringe. The reaction mixture was warmed up to room temperature and stirred for 4 hours. Then, it was cooled down to −75°, and 1,2-dibromoethane was added via syringe. The reaction mixture was then warmed to room temperature and stirred for 16 hours. The resulting reaction mixture was evaporated and purified by column chromatography on a silica gel eluted with heptanes/DCM 3/1 (v/v) to yield 2-bromo-3-methoxyphenanthrene (2.65 g, 70% yield).

In a nitrogen flushed 500 mL two-necked round-bottomed flask, 2-bromo-3-methoxyphenanthrene (8.9 g, 31.0 mmol), (3-chloro-2-fluorophenyl)boronic acid (9.73 g, 55.8 mmol), and potassium phosphate tribasic hydrate (21.41 g, 93 mmol) were dissolved in a DME (80 ml)/toluene (80 ml) mixture under nitrogen to give a colorless suspension. Tris(dibenzylideneacetone)dipalladium(0) (0.568 g, 0.620 mmol) and dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphane (SPhos, 1.018 g, 2.479 mmol) were added to the reaction mixture in one portion. The reaction mixture was degassed and heated to reflux under nitrogen for 16 hours. The reaction mixture was then cooled down, filtered through a silica gel and evaporated. The crude product was added to a silica gel column eluted with heptanes/DCM 3/1 (v/v) to yield 2-(3-chloro-2-fluorophenyl)-3-methoxyphenanthrene (8.5 g, 25.2 mmol, 81% yield) as a white solid.

In a nitrogen flushed 500 mL round-bottomed flask, 2-(3-chloro-2-fluorophenyl)-3-methoxyphenanthrene (7.85 g, 23.31 mmol) was dissolved in DCM (100 ml) under nitrogen to give a colorless solution. The reaction mixture was cooled to −20° C. with a dry ice/acetonitrile bath. A 1 M solution of tribromoborane in DCM (46.6 ml, 46.6 mmol) was added to the reaction mixture over 30 min. The reaction mixture was allowed to warm to room temperature and was stirred for 14 hours. The reaction mixture was carefully quenched with cold water, diluted with DCM, and washed with water. The organic solution was dried over sodium sulfate, filtered and concentrated. The crude product was added to a silica gel column and eluted with heptanes/ethyl acetate 1/1 (v/v) to give 2-(3-chloro-2-fluorophenyl)phenanthren-3-ol (6.2 g, 19.21 mmol, 82% yield) as a yellow solid.

2-(3-Chloro-2-fluorophenyl)phenanthren-3-ol (12 g, 37 mmol) and potassium carbonate (10.3 g, 2 eq.) were suspended in 100 mL of N-methylpyrrolidone (NMP), degassed and heated to 120° C. for 14 hours. About half of the NMP solvent was then evaporated and the reaction mixture was diluted with 10% aq. solution of LiCl. The product was precipitated from the reaction mixture and was then filtered off. It was purified by column chromatography on silica gel column and eluted with heptanes/DCM 7/3 (v/v) to obtain 1-chlorophenanthro[3,2-b]benzofuran (9.1 g, 81% yield).

1-Chlorophenanthro[3,2-b]benzofuran (3.0 g, 9.9 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (4.03 g, 16 mmol) and potassium acetate (1.94 g, 20 mmol) were suspended in 100 mL of dry dioxane. Tris(dibenzylideneacetone)dipalladium(0) (181 mg, 2 mol. %) and dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphane (SPhos, 325 mg, 4 mol. %) were added as one portion. The reaction mixture was degassed and heated to reflux under nitrogen for 16 hours. The reaction mixture was cooled to room temperature, and potassium phosphate tribasic hydrate (4.56 g, 19.8 mmol), 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)pyridine (1.84 g, 9.9 mmol), 10 mL of water, tetrakis(triphenylphosphine)palladium(0) (229 mg, 2 mol. %) and 75 mL of DMF were added.

The reaction mixture was degassed and immersed in an oil bath at 90° C. for 16 hours. The reaction mixture was then cooled to room temperature, diluted with water, and extracted with ethyl acetate. The organic extracts were combined, dried over anhydrous sodium sulfate, filtered and evaporated. The resulting material was purified on a silica gel column eluted with heptanes/ethyl acetate 3-20% gradient mixture to obtain pure 4-(2,2-dimethylpropyl-1,1-d2)-2-(phenanthro[3,2-b]benzofuran-11-yl)pyridine (1.9 g, 47% yield).

4-(2,2-Dimethylpropyl-1,1-d2)-2-(phenanthro[3,2-b]benzofuran-11-yl)pyridine (1.62 g, 1.8 eq.) was dissolved in 75 mL of 2-ethoxyethanol/DMF mixture (1/1, v/v) at room temperature and the iridium complex triflic salt (1.44 g, 1.0 eq.) shown above was added as one portion. The reaction mixture was degassed and immersed in the oil bath at 100° C. for 7 days. The reaction mixture was cooled down, diluted with water and a yellow precipitate was filtered off. The precipitate was washed with water, methanol and heptanes and dried in vacuo. The residue was subjected to column chromatography on a silica gel column eluted with heptanes/toluene/DCM mixture (70/15/15, v/v/v) to yield the target complex as bright yellow solid. Additional crystallization from toluene/heptanes provided 1.2 g (49% yield) of pure target material, IrL_(X79)(L_(B463))₂.

Compound IrL_(X588-5)(L_(B126))₂, below, was prepared by the same method with 45% yield at the last step:

Synthesis of IrL_(X588-7)(L_(B11))₂

((2′-Methoxy-[1,1′-biphenyl]-2-yl)ethynyl)trimethylsilane (18 g, 64 mmol) was dissolved in 120 ml of THF and 1 N solution of tetra-n-butylammonium fluoride (TBAF) in THF (2 equivalents) was added dropwise. The reaction mixture was stirred for 12 hours at room temperature, diluted with water and extracted with ethyl acetate. The organic phase was dried over sodium sulfate, filtered and evaporated, providing 2-ethynyl-2′-methoxy-1,1′-biphenyl (13 g, 97% yield).

2-Ethynyl-2′-methoxy-1,1′-biphenyl (11.7 g, 56 mmol) and platinum (II) chloride (1.5 g, 0.1 eq.) were suspended in 250 mL of toluene and heated to reflux for 14 hours. The toluene was evaporated and the crude material was purified by column chromatography on a silica gel column, eluted with heptanes/DCM 9/1 (v/v), providing 4-methoxyphenanthrene (8.7 g, 74% yield).

4-Methoxyphenanthrene (8.7 g, 42 mmol) was dissolved in 130 mL of dry THF under nitrogen atmosphere, added 0.5 mL of tetramethylethylenediamine (TMEDA) and solution was cooled in the isopropanol (IPA)/dry ice cooling bath. N-Butyl lithium (1.6 M solution in THF, 2 eq.) was added dropwise, and the reaction mixture was stirred for 2 hours at −78° C. 1,2-Dibromoethane (19.6 g, 2.5 eq.) in 20 mL of dry THF was added dropwise and the reaction mixture was allowed to warm up to room temperature. It was concentrated on the rotovap, diluted with water and extracted with DCM. The organic phase was evaporated, and the residue was purified by column chromatography on a silica gel column, eluted with heptanes/DCM gradient mixture. 3-Bromo-4-methoxyphenanthrene (9.2 g, 77% yield) was obtained as white solid.

3-Bromo-4-methoxyphenanthrene (15.0 g, 52 mmol), (3-chloro-2-fluorophenyl)boronic acid (9.11 g, 52 mmol), tris(dibenzylideneacetone)dipalladium(0) (Pd₂(dba)₃) (957 mg, 2 mol. %), dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphane (SPhos, 1716 mg, 8 mol. %) and potassium phosphate tribasic hydrate (24.06 g, 104 mmol) were suspended in the 250 mL of dimethoxyethane (DME) and 50 mL of water mixture. The reaction mixture was degassed and heated to reflux under nitrogen for 14 hours. It was then cooled down to room temperature, diluted with ethyl acetate and washed with water. The organic solution was dried over anhydrous sodium sulfate, filtered and evaporated. The residue was subjected to column chromatography on a silica gel column, eluted with heptanes/ethyl acetate 5-10% gradient mixture, to yield 3-(3-chloro-2-fluorophenyl)-4-methoxyphenanthrene as white solid (14.8 g, 84% yield).

3-(3-Chloro-2-fluorophenyl)-4-methoxyphenanthrene (20 g, 59.4 mmol) was dissolved in 300 mL of DCM at room temperature. A 1M solution of boron tribromide in DCM (2 equivalents) was added dropwise and the reaction mixture was stirred at room temperature for 14 hours. The reaction mixture was quenched with water, then washed with water and sodium bicarbonate solution. The organic solution was dried and evaporated, and the residue was purified by column chromatography on a silica gel column, eluted with heptanes/ethyl acetate 1/1 (v/v), to yield pure 3-(3-chloro-2-fluorophenyl)phenanthren-4-ol (12.0 g, 59% yield).

In an oven-dried 250 mL round-bottomed flask, 3-(3-chloro-2-fluorophenyl)phenanthren-4-ol (5.5 g, 17.04 mmol) and potassium carbonate (4.71 g, 34.1 mmol) were dissolved in N-methylpyrrolidone (NMP) (75 ml) under nitrogen to give a reddish suspension. The reaction mixture was degassed and heated to 120° C. for 10 hours. The reaction mixture was then cooled to room temperature, diluted with water, stirred and filtered. The precipitate was washed with water, ethanol, and heptanes. Crystallization of the precipitate from DCM/heptanes provided 12-chlorophenanthro[4,3-b]benzofuran (4.0 g, 78% yield).

12-Chlorophenanthro[4,3-b]benzofuran (5 g, 16.5 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (8.4 g, 33 mmol) and potassium acetate (3.24 g, 33 mmol) were suspended in 120 mL of dry dioxane. Tris(dibenzylideneacetone)dipalladium(0) (151 mg, 1 mol. %) and dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphane (Sphos, 271 mg, 4 mol. %) were added as one portion. The reaction mixture was degassed and heated to reflux under nitrogen for 16 hours.

The reaction mixture was cooled down, added potassium phosphate tribasic hydrate (11.4 g, 3 equivalents), 10 mL of water, tetrakis(triphenylphosphine)palladium(0) (382 mg, 2 mol. %), 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine (3.68 g, 18.2 mmol) and 75 mL of dimethylformamide (DMF). The reaction mixture was degassed and immersed in the oil bath at 90° C. for 16 hours. The reaction mixture was then cooled down, diluted with water and extracted multiple times with ethyl acetate. The organic extracts were combined, dried over sodium sulfate anhydrous, filtered and evaporated. The resultant product was purified on a silica gel column, eluted with heptanes/ethyl acetate gradient mixture to yield pure 4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)-2-(phenanthro[4,3-b]benzofuran-12-yl)pyridine (2.8 g, 39% yield).

The iridium complex triflic salt shown above (2.1 g, 2.447 mmol) and 4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)-2-(phenanthro[4,3-b]benzofuran-12-yl)pyridine (1.915 g, 4.41 mmol) were suspended together in a DMF (25 mL)/ethoxyethanol (25 mL) mixture, which was then degassed and heated in an oil bath at 100° C. for 10 days. The reaction mixture was cooled down, diluted with EtOAc (200 mL), washed with water and evaporated to obtain a crude product. The crude product was added to a silica gel column and was eluted with heptanes/DCM/toluene 70/15/15 to 60/20/20 (v/v/v) gradient mixture to yield the target compound, IrL_(X114)(L_(B461))₂ (1.1 g, 1.020 mmol, 41.7% yield) as a yellow solid.

Synthesis of IrL_(X588-13)(L_(B134))₂

Dibenzo[b,d]furan-4-ylboronic acid (10 g, 47.2 mmol), 2,2′-dibromo-1,1′-biphenyl (22.07 g, 70.8 mmol), sodium carbonate (12.50 g, 118 mmol), dimethoxyethane (DME) (200 ml), and water (40 ml) were combined in a flask. The reaction mixture was purged with nitrogen for 15 minutes, then tetrakis(triphenylphosphine)palladium(0) (1.635 g, 1.415 mmol) was added. The reaction mixture was heated in an oil bath set at 90° C. or 16 hours. The reaction mixture was then transferred to a separatory funnel and was extracted twice with ethyl acetate. The combined organics were washed with brine once, dried with sodium sulfate, filtered, and concentrated down to a brown oil. The brown oil was purified on a silica gel column, using 95/5 to 90/10 heptanes/DCM (v/v) to get a clear solidified oil of 4-(2′-bromo-[1,1′-biphenyl]-2-yl)dibenzo[b,d]furan (11.25 g, 59.7% yield).

4-(2′-Bromo-[1,1′-biphenyl]-2-yl)dibenzo[b,d]furan (11.25 g, 28.2 mmol) was dissolved in 240 mL of toluene and purged with nitrogen for 15 min. Cesium carbonate (22.03 g, 67.6 mmol), tris(3,5-bis(trifluoromethyl)phenyl)phosphane (1.889 g, 2.82 mmol) and bis-(benzonitrile) dichloloropalladium (II) (0.540 g, 1.409 mmol) were added, and the resulting reaction mixture was heated under nitrogen in an oil bath set at 115° C. for 16 hours. The reaction was filtered through silica gel, which was washed with ethyl acetate, then the combined organic solution was concentrated down to a brown solid.

The brown solid was purified on a silica gel column, eluted with 85/15 to 75/25 heptanes/DCM (v/v) to get triphenyleno[1,2-b]benzofuran as an off-white solid. The solid was dissolved in DCM, the heptane was added and the solution was partially concentrated down using a Rotovap at 30° C. The solids were then filtered off as a fluffy white solid. The solid was dried in the vacuum for 16 hours to get triphenyleno[1,2-b]benzofuran (3.9 g, 43.5% yield).

Triphenyleno[1,2-b]benzofuran (3.37 g, 10.59 mmol) was placed in a flask and the system was purged with nitrogen for 30 min. Tetrahydrofuran (THF) (150 ml) was added, then the solution was cooled in a dry ice/acetone bath for 30 min. The reaction changed to a white suspension and sec-butyllithium (13.23 ml, 18.52 mmol) 1.4 M solution in THF was added with the temperature below −60° C. The reaction turned black. After 2.5 hours, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.32 ml, 21.17 mmol) was added all at once. The reaction mixture was allowed to warm up in an ice bath for 2 hours. Then, the reaction was quenched with water, brine was added, and the aqueous phase was extracted twice with EtOAc. The combined organics were washed with brine, then dried over sodium sulfate, filtered and concentrated down to obtain 4,4,5,5-tetramethyl-2-(triphenyleno[1,2-b]benzofuran-14-yl)-1,3,2-dioxaborolane as white solid (4.5 g, 96% yield).

4,4,5,5-Tetramethyl-2-(triphenyleno[1,2-b]benzofuran-14-yl)-1,3,2-dioxaborolane (4.5 g, 10.13 mmol), 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine (2.156 g, 10.63 mmol), and potassium phosphate monohydrate (6.45 g, 30.4 mmol) were suspended in 1,4-dioxane (120 ml) and water (30.0 ml). The reaction mixture was purged with nitrogen for 15 minutes then tetrakis(triphenylphosphine)palladium(0) (0.351 g, 0.304 mmol) was added. The reaction was heated in an oil bath set at 100° C. for 16 hours. The resulting reaction mixture was partially concentrated down on the rotovap, then diluted with water and extracted with DCM. The combined organics were washed with water once, dried over sodium sulfate, filtered and concentrated down to a light brown solid. The light brown solid was purified on a silica gel column eluting with 98.5/1.5 to 98/2 DCM/EtOAc gradient mixture providing 5.1 g of a white solid. The 5.1 g sample was dissolved in 400 ml of hot DCM, then EtOAc was added and the resulting mixture was partially concentrated down on the rotovap with a bath set at 30° C. The precipitate was filtered off and dried in the vacuum oven for 16 hours to obtain 4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)-2-(triphenyleno[1,2-b]benzofuran-14-yl)pyridine as white solid (3.1 g, 63.2% yield).

The iridium complex triflic salt shown above (2.2 g, 2.123 mmol) and 4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)-2-(triphenyleno[1,2-b]benzofuran-14-yl)pyridine (1.852 g, 3.82 mmol) were suspended in the mixture of DMF (25 ml) and 2-ethoxyethanol (25.00 ml). The reaction mixture was purged with nitrogen for 15 minutes then heated to 80° C. under nitrogen for 3.5 days. The resulting mixture was concentrated on the rotovap, cooled down, then diluted with methanol. A brown-yellow precipitate was filtered off, washed with methanol then recovered the solid using DCM. The solid was purified on a silica gel column eluting with 50/50 to 25/75 heptanes/toluene gradient mixture to get 2.2 g of a yellow solid. The yellow solid was further purified on a basic alumina column using 70/30 to 40/60 heptanes/DCM (v/v) to get 1.8 g of a yellow solid. The solid was dissolved in DCM, mixed with 50 ml of toluene and 300 ml of isopropyl alcohol, then partially concentrated down on the rotovap. The precipitate was filtered off and dried for 3 hours in the vacuum oven to get target complex as bright yellow solid IrL_(X206)(L_(B467))₂ (1.23 g, 44.3% yield).

Synthesis of IrL_(X588-20)(L_(B188))₂

2-iodo-1,3-dimethoxybenzene (16 g, 60.6 mmol), (3-chloro-2-fluorophenyl)boronic acid (12.15 g, 69.7 mmol), tris(dibenzylideneacetone)palladium(0) (1.109 g, 1.212 mmol) and SPhos (2.73 g, 6.67 mmol) were charged into a reaction flask with 300 mL of toluene. Potassium phosphate tribasic monohydrate (41.8 g, 182 mmol) was then added to the reaction mixture. This mixture was degassed with nitrogen then was stirred and heated in an oil bath set at 115° C. for 47 hours. The reaction mixture was cooled down to room temperature, then washed with water. The organic phase was dried over magnesium sulfate then filtered and concentrated in vacuo. The crude residue was passed through a silica gel column eluting with 15-25% DCM in heptanes. After evaporation, pure product fractions yielded 3-chloro-2-fluoro-2′,6′-dimethoxy-1,1′-biphenyl (8.5 g, 31.9 mmol, 52.6% yield) as a white solid.

3-Chloro-2-fluoro-2′,6′-dimethoxy-1,1′-biphenyl (8.5 g, 31.9 mmol) was dissolved in 75 mL of DCM. This solution was cooled in a wet ice bath, and a 1 M solution of boron tribromide in DCM (130 ml, 130 mmol) was added dropwise. Stirring was continued as the reaction mixture was allowed to gradually warm up to room temperature over 16 hours. The reaction mixture was poured into a beaker of wet ice. A solid was collected via filtration. The filtrate was separated, dissolved in DCM and the solution was dried over magnesium sulfate. This solution was then filtered and concentrated in vacuo yielding 3′-chloro-2′-fluoro-[1,1′-biphenyl]-2,6-diol (7.45 g, 31.2 mmol, 98% yield) as a white solid.

3′-Chloro-2′-fluoro-[1,1′-biphenyl]-2,6-diol (7.45 g, 31.2 mmol) and potassium carbonate (9.49 g, 68.7 mmol) were charged into the reaction flask with 70 mL of NMP. This reaction mixture was heated at 130° C. for 18 hours. Heating was discontinued. The reaction mixture was diluted with 200 mL of water, then extracted with DCM. The extracts were combined, washed with aqueous LiCl, dried over magnesium sulfate, filtered and the solvent was evaporated in vacuo. This crude residue was subjected to a bulb-bulb distillation to remove NMP. The remaining residue was passed through a silica gel column eluted with 70-80% DCM in heptanes. Pure fractions were combined and concentrated in vacuo. The solid was then triturated with heptanes. A tan solid was collected via filtration and then was dried yielding 6-chlorodibenzo[b,d]furan-1-ol (5.6 g, 25.6 mmol, 82% yield).

6-Chlorodibenzo[b,d]furan-1-ol (5.55 g, 25.4 mmol) was dissolved in DCM. Pyridine (5.74 ml, 71.1 mmol) was added to this reaction mixture as one portion. The homogeneous solution was cooled to 0° C. using a wet ice bath. Trifluoromethanesulfonic anhydride (10.03 g, 35.5 mmol) was dissolved in 20 mL of DCM and was added dropwise to the cooled reaction mixture. Stirring was continued as the reaction mixture was allowed to gradually warm up to room temperature over 16 hours. The reaction mixture was washed with aqueous LiCl, dried over magnesium sulfate, filtered and concentrated in vacuo. The crude product was passed through silica gel column eluting with 5-30% DCM in heptanes. The Pure product fractions were combined and concentrated yielding 6-chlorodibenzo[b,d]furan-1-yl trifluoromethanesulfonate (8.9 g, 25.4 mmol, 100% yield) as a white solid.

6-Chlorodibenzo[b,d]furan-1-yl trifluoromethanesulfonate (10 g, 28.5 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (9.41 g, 37.1 mmol), potassium acetate (6.43 g, 65.6 mmol) and [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (0.93 g, 1.14 mmol) were charged into the reaction flask with 250 mL of dioxane. This mixture was degassed with nitrogen then heated to reflux for 14 hours. Heating was discontinued. The solvent was evaporated, then the crude product was partitioned with 500 mL water and 200 mL DCM. The organic solution was dried over magnesium sulfate then filtered and concentrated in vacuo. The crude product was passed through a silica gel column eluting with 20-35% DCM in heptanes. Pure product fractions were combined and concentrated in vacuo yielding 2-(6-chlorodibenzo[b,d]furan-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6.9 g, 21.00 mmol, 73.6% yield) as a solid.

2-(6-Chlorodibenzo[b,d]furan-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7.5 g, 22.82 mmol), ((2-bromophenyl)ethynyl)trimethylsilane (7.34 g, 29.0 mmol) and tetrakis(triphenylphosphine)palladium(0) (1.07 g, 0.927 mmol) were charged into a reaction flask with 150 mL of DME. Potassium carbonate (9.5 g, 68.8 mmol) was dissolved in 15 mL of water then was added all at once to the reaction mixture. This reaction mixture was degassed with nitrogen, then heated to reflux for 18 hours. The reaction mixture was cooled to room temperature, then the solvent was removed in vacuo. The crude product was partitioned between 200 mL of DCM and 100 mL of water. The aqueous phase was extracted with DCM. The DCM extracts were combined, dried over magnesium sulfate, then filtered and concentrated in vacuo. The crude product was passed through a silica gel column with 7-12% DCM in heptanes. Pure product fractions were combined and concentrated in vacuo yielding ((2-(6-chlorodibenzo[b,d]furan-1-yl)phenyl)ethynyl)trimethylsilane (7.35 g, 19.60 mmol, 86% yield) as a viscous yellow oil that solidified upon standing overnight.

((2-(6-Chlorodibenzo[b,d]furan-1-yl)phenyl)ethynyl)trimethylsilane (13.95 g, 37.2 mmol) was dissolved in 100 mL of THF. This solution was stirred at room temperature as a 1 M solution of tetrabutylammonium fluoride (TBAF) in THF (45 ml, 45.0 mmol) was added to the reaction mixture over a 5 minute period. The reaction was slightly exothermic, but no cooling was required. Stirring was continued at room temperature for 4 hours. The reaction mixture was diluted with 200 mL of water, then it was extracted with DCM. The extracts were combined, dried over magnesium sulfate, filtered and concentrated in vacuo. The crude residue was passed through silica gel column eluting with 10-15% DCM in heptanes to yield ethynylphenyl)dibenzo[b,d]furan (9.6 g, 31.7 mmol, 85% yield) as a white solid.

Platinum(II) chloride (0.527 g, 1.982 mmol) was charged into a reaction flask with 50 mL of toluene. 6-Chloro-1-(2-ethynylphenyl)dibenzo[b,d]furan (5 g, 16.51 mmol) was then added to the reaction flask followed by 100 mL of toluene. This mixture was degassed with nitrogen then heated in an oil bath set at 93° C. for 24 hours. Heating was discontinued. The reaction mixture was passed through a pad of silica gel. The toluene filtrate was concentrated under vacuum. This crude residue was passed through silica gel column eluting with 10-15% DCM in heptanes. Pure product fractions were combined and concentrated in vacuo yielding 10-chlorophenanthro[3,4-b]benzofuran (3.2 g, 10.57 mmol, 64.0% yield) as a white solid.

10-Chlorophenanthro[3,4-b]benzofuran (3.25 g, 10.73 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (3.54 g, 13.96 mmol), potassium acetate (2.63 g, 26.8 mmol), tris(dibenzylideneacetone) palladium(0) (0.246 g, 0.268 mmol), and SPhos (0.682 g, 1.664 mmol) were charged into a reaction flask with 140 mL of dioxane. This mixture was degassed with nitrogen then heated to reflux for 18 hours. The heating was discontinued. The reaction mixture was used for the next step without purification.

2-Chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine (2.98 g, 14.70 mmol), tetrakis(triphenylphosphine)palladium(0) (0.743 g, 0.644 mmol), potassium phosphate tribasic monohydrate (7.40 g, 32.2 mmol), and 20 mL of water were added to the reaction mixture from previous step. This mixture was degassed with nitrogen then heated to reflux for 18 hours. The reaction mixture was cooled down to room temperature. The dioxane was removed under vacuum. The crude residue was diluted with 100 mL of water then was extracted with DCM. The extracts were dried over magnesium sulfate, filtered, and concentrated. The crude residue was passed through a silica gel column eluting with 0.5-2% ethyl acetate in DCM to yield 4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)-2-(phenanthro[3,4-b]benzofuran-10-yl)pyridine (3.2 g, 7.36 mmol, 68.6% yield) as a white solid.

4-(2,2-Dimethylpropyl-1,1-d2)-5-(methyl-d3)-2-(phenanthro[3,4-b]benzofuran-10-yl)pyridine (1.773 g, 4.08 mmol) and the iridium complex triflic salt shown above (2 g, 2.331 mmol) were charged into a reaction flask with 40 mL of 2-ethoxyethanol and 40 mL of DMF. This mixture was degassed with nitrogen then heated in an oil bath set at 100° C. for 10 days. Heating was discontinued and the solvent was removed in vacuo. The crude residue was then triturated with 150 mL of methanol. A solid was isolated via filtration. This material was dried under vacuum then was dissolved in 80% DCM in heptanes and was passed through 10 inches of activated basic alumina. The alumina column was eluted with 80% DCM in heptanes. The pure product fractions were combined and concentrated in vacuo yielding 2.6 g of a yellow solid. This solid was then passed through a silica gel column eluting with 35-60% toluene in heptanes. The material was subjected to a second chromatographic purification on the silica gel column eluted with 35% toluene in heptanes. The pure fractions were combined, concentrated in vacuo, then triturated with methanol. A bright yellow solid was collected via filtration yielding the desired iridium complex, IrL_(X33)(L_(B461))₂ (1.45 g, 1.344 mmol, 57.7% yield)

Synthesis of IrL_(X588-18)(L_(B134))₂

Triphenylphosphine (0.974 g, 3.71 mmol), diacetoxypalladium (0.417 g, 1.856 mmol), potassium carbonate (10.26 g, 74.3 mmol), 2-bromo-2′-iodo-1,1′-biphenyl (13.33 g, 37.1 mmol) and 2-(6-chlorodibenzo[b,d]furan-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (12.2 g, 37.1 mmol) were suspended in a ethanol (65 ml)/enonitrile (130 ml) mixture. The reaction mixture was degassed and heated at 35° C. under nitrogen atmosphere for 16 hours. The reaction mixture was cooled down to room temperature, then filtered through a silica gel plug that was washed with EtOAc. The filtrate was evaporated. Dichloromethane was added and the resulting mixture was washed with water, dried and evaporated leaving a dark brown semi-solid that was absorbed onto a silica gel and chromatographed on silica gel eluting with 98% heptane/2% THF. The impurities were eluted with this eluant. The eluant was changed to 100% DCM and pure product was eluted from the silica gel yielding 1-(2′-bromo-[1,1′-biphenyl]-2-yl)-6-chlorodibenzo[b,d]furan (8.8 g, 20.3 mmol, 54.66% yield).

1-(2′-bromo-[1,1′-biphenyl]-2-yl)-6-chlorodibenzo[b,d]furan (3 g, 6.92 mmol), tris(3,5-bis(trifluoromethyl)phenyl)phosphane (0.695 g, 1.038 mmol), cesium carbonate (5.40 g, 16.60 mmol) and bis(benzonitrile)palladium(II) chloride (0.199 g, 0.519 mmol) were charged into a reaction flask with 125 mL of o-xylene. This mixture was degassed with nitrogen then heated in an oil bath at 148° C. for 18 hours. The reaction mixture was cooled down to room temperature. Gas chromatography/mass spectroscopy (GC/MS) analysis showed about 15% of the product formed. Palladium catalyst (0.4 g) and 1.5 g of triarylphosphine were added to the reaction mixture. This mixture was degassed with nitrogen, then heated in a bath at 148° C. for 2½ days. The reaction mixture was cooled to room temperature. GC/MS analysis showed no starting material. This mixture was filtered through a thin pad of silica gel. The pad was rinsed with toluene. The toluene/xylene filtrate was concentrated in vacuo. This crude product was absorbed onto a silica gel then passed through a silica gel column eluted with 15-18% DCM/heptanes. The product fractions were combined and concentrated in vacuo to near dryness. This material was then triturated with heptanes. A white solid was collected via filtration yielding 8-chlorotriphenyleno[2,1-b]benzofuran (1.48 g, 4.19 mmol, 60.6% yield) as a white solid.

8-Chlorotriphenyleno[2,1-b]benzofuran (3.05 g, 8.64 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (2.96 g, 11.67 mmol), tris(dibenzylideneacetone)palladium(0) (0.21 g, 0.230 mmol) and SPhos (0.65 g, 1.585 mmol) were charged into a reaction flask with 100 ml of dioxane. Potassium acetate (2.25 g, 22.96 mmol) was then added to the reaction mixture. This mixture was degassed with nitrogen then heated to reflux for 20 hours. The reaction mixture was cooled down to room temperature and reaction mixture was used “as is” as a dioxane solution.

4,4,5,5-Tetramethyl-2-(triphenyleno[2,1-b]benzofuran-8-yl)-1,3,2-dioxaborolane (3.84 g, 8.64 mmol), 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine (2.452 g, 12.10 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.42 g, 0.364 mmol) were charged into a r mixture. Potassium phosphate tribasic monohydrate (5.96 g, 25.9 mmol) was then dissolved in 20 mL of water and added to the mixture. This reaction mixture was degassed with nitrogen then heated to reflux for 24 hours. The reaction mixture was cooled to room temperature and white precipitate formed. This mixture was diluted with 150 mL of water and the precipitate was collected via filtration then dissolved in 400 mL of DCM. This solution was dried over magnesium sulfate then filtered and evaporated. The crude residue was passed through silica gel column eluting with 100% DCM then 1-4% ethyl acetate/DCM. Pure product fractions were combined and concentrated in vacuo. This material was triturated with warm heptane. A white solid was collected via filtration then was dried in vacuo yielding 4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)-2-(triphenyleno[2,1-b]benzofuran-8-yl)pyridine (2.85 g, 5.88 mmol, 68.1% yield).

4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)-2-(triphenyleno[2,1-b]benzofuran-8-yl)pyridine (2.1 g, 4.33 mmol) and the iridium complex triflic salt show above (2.5 g, 2.412 mmol) were charged into the reaction flask with 60 mL of 2-ethoxyethanol and 60 mL of DMF. This reaction mixture was degassed with nitrogen then heated in an oil bath set at 100° C. for 8 days. Heating was discontinued and the solvents were evaporated in vacuo. The crude product was then triturated with methanol. A yellow solid was collected via filtration. This material was dissolved in a small amount of DCM and passed through an activated basic alumina column eluted with 30-40% DCM/heptanes. Column fractions were combined and concentrated in vacuo yielding 2.25 g of product. This material was passed through silica gel column eluted with 35-50% toluene in heptanes. The pure product fractions were combined and concentrated, then were triturated with methanol. A yellow solid was collected via filtration yielding IrL_(X220)(L_(B467))₂ (2.15 g, 1.643 mmol, 68.1% yield) as a yellow solid.

Synthesis of IrL_(X588-17)(L_(B130))₂

4,4,5,5-Tetramethyl-2-(triphenyleno[2,3-b]benzofuran-11-yl)-1,3,2-dioxaborolane (4.5 g, 10.13 mmol), 2-bromo-4,5-bis(methyl-d3)pyridine (3.12 g, 16.24 mmol), and tetrakis(triphenylphosphine)palladium(0) (0.584 g, 0.506 mmol) were charged into a reaction flask with 130 mL of 1,4-dioxane. Potassium phosphate tribasic monohydrate (6.99 g, 30.4 mmol) was then dissolved in 20 mL of water and added to the reaction mixture. This mixture was degassed with nitrogen, then heated at reflux for 26 hours. A white precipitate was formed in the reaction mixture. Heating was discontinued and the reaction mixture was concentrated to near dryness, then diluted with 300 mL of water. A precipitate was collected via filtration then rinsed with water. This solid was then suspended in 350 mL of DCM and was heated to reflux. This heterogeneous mixture was then cooled back to room temperature. A white solid was collected via filtration yielding 4,5-bis(methyl-d3)-2-(triphenyleno[2,3-b]benzofuran-11-yl)pyridine (2.7 g, 6.29 mmol, 62.1% yield)

4,5-Bis(methyl-d3)-2-(triphenyleno[2,3-b]benzofuran-11-yl)pyridine (2 g, 4.66 mmol) was dissolved in a mixture of 80 mL of 2-ethoxyethanol and 80 mL of DMF. The iridium complex triflic salt shown above (2.56 g, 2.55 mmol) was then added and the reaction mixture was degassed using nitrogen then was stirred and heated in an oil bath set at 103° C. for 12 days. The reaction mixture was cooled down to room temperature and a yellow solid was collected via filtration. This solid was dried in vacuo then was dissolved in 40% DCM in heptanes and was passed through a basic alumina column eluting the column with 40-50% DCM in heptanes. Product fractions were combined and concentrated. This material was then passed through a silica gel column eluting with 40-70% toluene in heptanes. Pure product fractions were combined and concentrated in vacuo. This material was triturated with methanol then filtered and dried in vacuo yielding the desired iridium complex, IrL_(X211)(L_(B466))₂ (1.25 g, 1.026 mmol, 40.2% yield) as a yellow solid.

Synthesis of Comparative Compound 1

3-Chloro-3′,6′-difluoro-2,2″-dimethoxy-1,1′:2′,1″-terphenyl (10.8 g, 29.9 mmol) was dissolved in DCM (400 ml) and then cooled to 0° C. A IN tribromoborane (BBr₃) solution in DCM (90 ml, 90 mmol) was added dropwise. The reaction mixture was stirred at 20° C. for 16 hours, then quenched with water and extracted with DCM. The combined organic phase was washed with brine. After the solvent was removed, the residue was subjected to column chromatography on a silica gel column eluted with DCM/heptanes gradient mixture to yield 3-chloro-3′,6′-difluoro-[1,1′:2′,1″-terphenyl]-2,2″-diol as white solid (4.9 g, 53% yield).

A mixture of 3-chloro-3′,6′-difluoro-[1,1′:2′,1″-terphenyl]-2,2″-diol (5 g, 15.03 mmol) and K₂CO₃ (6.23 g, 45.08 mmol) in 1-methylpyrrolidin-2-one (75 mL) was vacuumed and stored under nitrogen. The mixture was heated at 150° C. for 16 hours. After the reaction was cooled to 20° C., it was diluted with water and extracted with EtOAc. The combined organic phase was washed with brine. After the solvent was removed, the residue was subjected to column chromatography on a silica gel column eluted with 20% DCM in heptane to yield the target chloride as white solid (3.0 g, 68% yield).

The chloride molecule above (3 g, 10.25 mmol) was mixed with 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (5.21 g, 20.50 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.188 g, 0.205 mmol), dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphane (SPhos, 0.337 g, 0.820 mmol), and potassium acetate (“KOAc”)(2.012 g, 20.50 mmol) and suspended in 1,4-dioxane (80 ml). The mixture was degassed and heated at 100° C. for 16 hours. The reaction mixture was cooled to 20° C. before being diluted with 200 mL of water and extracted with EtOAc (3 times by 50 mL). The combined organic phase was washed with brine. After the solvent was evaporated, the residue was purified on a silica gel column eluted with 2% EtOAc in DCM to yield the target boronic ester as white solid (3.94 g, 99% yield).

The boronic ester from above (3.94 g, 10.25 mmol), 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine (3.12 g, 15.38 mmol) and sodium carbonate (2.72 g, 25.6 mmol) were suspended in the mixture of DME (80 ml) and water (20 ml). The reaction mixture was degassed and tetrakis(triphenylphosphine)palladium(0) (0.722 g, 0.625 mmol) was added as one portion. The mixture was heated at 100° C. for 14 hours. After the reaction was cooled to 20° C., it was diluted with water and extracted with EtOAc. The combined organic phase was washed with brine. After the solvent was evaporated, the residue was subjected to column chromatography on a silica gel column eluted with 2% EtOAc in DCM to yield the target ligand as a white solid (1.6 g, 37% yield)

The iridium complex triflic salt shown above (1.7 g) and the target ligand from the previous step (1.5 g, 3.57 mmol) were suspended in the mixture of 2-ethoxyethanol (35 ml) and DMF (35 ml). The mixture was degassed for 20 minutes and was heated to reflux (90° C.) under nitrogen for 18 hours. After the reaction was cooled to 20° C., the solvent was evaporated. The residue was dissolved in DCM and the filtered through a short silica gel plug. The solvent was evaporated, and the residue was subjected to column chromatography on a silica gel then eluted with a mixture of DCM and heptane (7/3, v/v) to yield the comparative compound 1 as yellow crystals (0.8 g, 38% yield).

Synthesis of Comparative Compound 2

Sodium carbonate (11.69 g, 110 mmol), 1,4-dibromo-2,3-difluorobenzene (15 g, 55.2 mmol), (2-methoxyphenyl)boronic acid (8.80 g, 57.9 mmol) and tetrakis(triphenylphosphine)palladium(0) (3.19 g, 2.76 mmol) were suspended in a water (140 mL)/dioxane (140 mL) mixture. The reaction mixture was degassed, heated in a 80° C. oil bath for 20 hours and allowed to cool. The resulting mixture was mixed with brine and extracted with EtOAc. The extracts were washed with water and brine, then dried and evaporated leaving a solid/liquid mixture that was absorbed onto a silica gel and chromatographed on silica gel column eluted with heptane followed by heptanes/DCM 4/1 (v/v), providing 12.5 g of the target structure as a colorless liquid (76% yield).

Sodium carbonate (8.77 g, 83 mmol), tetrakis(triphenylphosphine)palladium(0) (1.435 g, 1.242 mmol), 4-bromo-2,3-difluoro-2′-methoxy-1,1′-biphenyl (12.38 g, 41.4 mmol) and (3-chloro-2-methoxyphenyl)boronic acid (8.10 g, 43.5 mmol) were suspended in a water (125 mL)/dioxane (125 mL) mixture. The reaction mixture was degassed and heated in a 80° C. oil bath for 20 hours. Then additional catalyst (1.435 g, 1.242 mmol) and boronic acid (2.4 g, 0.3 equivalents) were added and the reaction mixture was degassed again and heated in a 80° C. oil bath under nitrogen for 12 hours. The reaction mixture was allowed to cool before being diluted with brine and extracted with DCM. The extracts were washed with water and brine, then dried and evaporated leaving 23.7 g of white solid that was purified by column chromatography on silica gel, eluted with heptane/DCM gradient mixture, providing 9.95 g of the target material as a white solid (67% yield).

A solution of 3-chloro-2′,3′-difluoro-2,2″-dimethoxy-1,1′:4′,1″-terphenyl (9.95 g, 27.6 mmol) in DCM (150 mL) was cooled in an ice/salt bath and a 1M solution of boron tribromide in DCM (110 mL, 110 mmol) was added dropwise. The reaction mixture was stirred for 14 hours and allowed to slowly warm up to room temperature. The reaction mixture was then cooled in an ice bath and 125 mL of water was added dropwise. The resulting mixture was stirred for 30 minutes, then extracted with DCM and then EtOAc. The extracts were washed with water, dried and evaporated providing 8.35 g of white solid (91% yield).

3-Chloro-2′,3′-difluoro-[1,1′:4′,1″-terphenyl]-2,2″-diol (8.35 g, 25.10 mmol) and potassium carbonate (7.63 g, 55.2 mmol) were suspended under nitrogen in N-Methyl-2-pyrrolidinone (100 mL) and heated to 130° C. in an oil bath for 16 hours. The reaction mixture was allowed to cool and the solvent was distilled off. The residue was chromatographed on silica gel column and eluted with heptanes/ethyl acetate 9/1 (v/v), providing the target chloride as a white solid (6.5 g, 88% yield).

The chloride from the previous step (6.5 g, 22.21 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (11.28 g, 44.4 mmol), and ethoxy-[1,1′-biphenyl]-2-yl)phosphane (SPhos, 0.547 g, 1.332 mmol) and tris(dibenzylideneacetone)dipalladium(0) (0.305 g, 1.5 mol. %) were dissolved in dioxane (250 mL) he reaction mixture was degassed and heated to reflux under nitrogen for 18 hours. The reaction mixture was allowed to cool before it was diluted with water and extracted with EtOAc. The extracts were combined, washed with water, dried and evaporated leaving an orange semi-solid. The orange semi-solid was tritiarated with heptane and the solid was filtered off to yield 7.3 g of the target boronic ester (85% yield).

The boronic ester from the previous step (3.6 g, 9.37 mmol), 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine (1.899 g, 9.37 mmol), and tetrakis(triphenyl)phosphine)palladium(0) (0.541 g, 0.468 mmol) were suspended in dioxane (110 ml). Potassium phosphate tribasic monohydrate (6.46 g, 28.1 mmol) in water (20 mL) was added as one portion. The reaction mixture was degassed and heated to reflux under nitrogen for 24 hours. The reaction mixture was allowed to cool, before it was diluted with brine and extracted with ethyl acetate. The extracts were washed with brine, dried and evaporated leaving a solid that was absorbed onto a plug of silica gel and chromatographed on a silica gel column, eluted with heptanes/DCM 1/1 (v/v) then 5% methanol in DCM, to isolate the desired ligand as a white solid (3.17 g, 80% yield).

The ligand from the previous step (1.95 g, 4.59 mmol) was suspended in a 2-ethoxy ethanol (25 mL)/DMF (25 mL) mixture. The iridium complex triflic salt shown above (2.362 g, 2.55 mmol) was added as one portion. The reaction mixture was degassed and heated in a 100° C. oil bath under nitrogen for 9 days. The reaction mixture was allowed to cool, and the solvents were evaporated. The residue was tritiarated with methanol to recover 3.4 g of yellow solid, which was absorbed onto a silica gel plug and chromatographed on silica gel column, eluted with heptanes/toluene/DCM 6/3/1 (v/v/v) mixture. Additional purification on a silica gel column, eluted with heptanes/toluene 1/1 (v/v) solvents provided a bright yellow solid material, which was tritiarated with methanol, filtered and dried to yield 0.93 g of the pure iridium target material (comparative compound 2) shown above (19% yield).

Device Examples

All example devices were fabricated by high vacuum (<10⁻⁷ Torr) thermal evaporation. The anode electrode was 800 A of indium tin oxide (ITO). The cathode consisted of 1000 Å of Al. All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H₂O and O₂) immediately after fabrication, and a moisture getter was incorporated inside the package. The organic stack of the device examples consisted of sequentially, from the ITO surface, 100 Å of HATCN as the hole injection layer (HIL); 400 Å of HTL-1 as the hole transporting layer (HTL); 50 Å of EBL-1 as the electron blocking layer; 400 Å of an emissive layer (EML) comprising 12% of the dopant in a host comprising a 60/40 mixture of Host-1 and Host-2; 350 Å of Liq doped with 35% of ETM-1 as the ETL; and 10 Å of Liq as the electron injection layer (EIL).

Upon fabrication, the electroluminescence (EL) and current density-voltage-luminance (JVL) performance of the devices was measured. The device lifetimes were evaluated at a current density of 80 mA/cm². The device data are normalized to Comparative Example 1 and is summarized in Table 1. The device data demonstrates that the dopants of the present invention afford green emitting devices with better device lifetime than the comparative example. For example, comparing device example 1 vs 1′ and 2 vs 2′ it can be observed that replacing the dibenzofuran moiety with a phenanthrene moiety (see the following scheme) substantially increases the device lifetime (9 fold improvement for 1 vs 1′ and 6.2 fold improvement for 2 vs 2′). Furthermore, the narrowness of the emission spectrum substantially improves for the dopants of the present invention. For example, comparing device example 1 vs 1′, it can be observed that replacing the dibenzofuran moiety with phenanthrene moiety (see the following scheme) results in a decrease of the FWHM (Full width at half maximum) from 53 nm to 38 nm (1′ vs 1). In general, the dopants of the present invention have the FWHM less than 50 run (see device example 1,3,4,5,8 and 9). As known to the person skilled in the art, the device lifetime and the narrowness of the emission spectrum are two parameters that are very important to producing a commercially useful OLED device and are also some of the most difficult parameters to improve. In general, a few percent improvement is consider a significant improvement to those skilled in the OLED arts. In this invention, these two parameters unexpectedly have a huge improvement with one design change to the molecule.

TABLE 1 At 80 λ At 10 mA/cm² mA/cm2 Device 1931 CIE max FWHM Voltage EQE LT_(95%) Example Dopant x y [nm] [nm] [a.u.]* [a.u.]* [a.u.]* 1 IrL_(X588-20)(L_(B118))₂ 0.334 0.637 530 38 1.032 0.90 9 2 IrL_(X588-11) (L_(B132))₂ 0.340 0.631 526 57 0.982 1.06 11.2 3 IrL_(X588-5)(L_(B126))₂ 0.319 0.645 524 49 1.026 0.985 5.4 4 IrL_(X588-12)(L_(B118))₂ 0.325 0.645 530 24 0.978 0.757 13.5 5 IrL_(X588-35)(L_(B118))₂ 0.342 0.633 530 28 0.978 0.85 14.6 6 IrL_(X588-18)(L_(B134))₂ 0.355 0.624 532 52 1.036 1.06 12.9 7 IrL_(X588-13)(L_(B134))₂ 0.345 0.630 529 52 1.03 1.04 8.6 8 IrL_(X588-17)(L_(B130))₂ 0.322 0.645 526 31 1.03 0.929 16.9 9 IrL_(X588-7)(L_(B118))₂ 0.366 0.636 528 29 1.06 0.962 19.6 1′ Comparative 0.306 0.647 520 53 1 1 1 example 1 2′ Comparative 0.332 0.634 524 57 0.97 1.084 1.8 example 2 *Value is normalized to comparative example 1′ 

We claim:
 1. A compound comprising a first ligand L_(X) of Formula II

wherein, F is a 5-membered or 6-membered carbocyclic or heterocyclic ring; each R^(F) and R^(G) independently represents mono to the maximum possible number of substitutions, or no substitution; Z³ and Z⁴ are each independently C or N and coordinated to a metal M to form a 5-membered chelate ring; G is a fused ring structure comprising five or more fused heterocyclic or carbocyclic rings, of which at least one ring is of Formula III

the fused heterocyclic or carbocyclic rings in the fused ring structure G are 5-membered or 6-membered; of which if two or more 5-membered rings are present, at least two of the 5-membered rings are fused to one another; Y is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″; each R′, R″, R^(F), and R^(G) is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; the metal M can be coordinated to other ligands; and the ligand L_(X) can be linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand.
 2. The compound of claim 1, wherein the ligand L_(X) has a structure of Formula IV

wherein, A¹ to A⁴ are each independently C or N; one of A¹ to A⁴ is Z⁴ in Formula II; R^(H) and R¹ represents mono to the maximum possibly number of substitutions, or no substitution; ring H is a 5-membered or 6-membered aromatic ring; n is 0 or 1; when n is 0, A⁸ is not present, two adjacent atoms of A⁵ to A⁷ are C, and the remaining atom of A⁵ to A⁷ is selected from the group consisting of NR′, O, S, and Se; when n is 1, two adjacent of A⁵ to A⁸ are C, and the remaining atoms of A⁵ to A⁸ are selected from the group consisting of C and N, and adjacent substituents of R^(H) and R¹ join or fuse together to form at least two fused heterocyclic or carbocyclic rings; R¹ and each R^(H) and R^(I) is independently a hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; and any two substituents can be joined or fused together to form a ring.
 3. The compound of claim 2, wherein each R^(F), R^(H), and R^(I) is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinations thereof.
 4. The compound of claim 2, wherein the metal M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Au, and Cu.
 5. The compound of claim 2, wherein Y is O.
 6. The compound of claim 2, wherein n is
 1. 7. The compound of claim 2, wherein n is 1, A⁵ to A⁸ are each C, a first 6-membered ring is fused to A⁵ and A⁶, and a second 6-membered ring is fused to the first 6-membered ring but not ring H.
 8. The compound of claim 2, wherein the ring F is selected from the group consisting of pyridine, pyrimidine, pyrazine, imidazole, pyrazole, and N-heterocyclic carbene.
 9. The compound of claim 2, wherein the first ligand L_(X) is selected from the group consisting of:

wherein, Z⁷ to Z¹⁴ and, when present, Z¹⁵ to Z¹⁸ are each independently N or CR^(Q); each R^(Q) is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, and combinations thereof; and any two substituents may be joined or fused together to form a ring.
 10. The compound of claim 2, wherein the first ligand L_(X) is selected from the group consisting of L_(X1-1) to L_(X897-38) with the general numbering formula L_(Xh-m), and L_(X1-39) to L_(X1446-57) with the general numbering formula L_(Xi-n); wherein h is an integer from 1 to 897, i is an integer from 1 to 1446, m is an integer from 1 to 38 referring to Structure 1 to Structure 38, and n is an integer from 39 to 57 referring to Structure 39 to Structure 57; wherein for each L_(Xh-m); L_(Xh-I) (h=1 to 897) is based on Structure 1,

L_(Xh-2) (h=1 to 897) is based on Structure 2,

L_(Xh-3) (h=1 to 897) is based on Structure 3,

L_(Xh-4) (h=1 to 897) is based on Structure 4,

L_(Xh-5) (h=1 to 897) is based on Structure 5,

L_(Xh-6) (h=1 to 897) is based on Structure 6,

L_(Xh-7) (h=1 to 897) is based on Structure 7,

L_(Xh-8) (h=1 to 897) is based on Structure 8,

L_(Xh-9) (h=1 to 897) is based on Structure 9,

L_(Xh-10) (h=1 to 897) is based on Structure 10,

L_(Xh-11) (h=1 to 897) is based on Structure 11,

L_(Xh-12) (h=1 to 897) is based on Structure 12,

L_(Xh-13) (h=1 to 897) is based on Structure 13,

L_(Xh-14) (h=1 to 897) is based on Structure 14,

L_(Xh-15) (h=1 to 897) is based on Structure 15,

L_(Xh-16) (h=1 to 897) is based on Structure 16,

L_(Xh-17) (h=1 to 897) is based on Structure 17,

L_(Xh-18) (h=1 to 897) is based on Structure 18,

L_(Xh-19) (h=1 to 897) is based on Structure 19,

L_(Xh-20) (h=1 to 897) is based on Structure 20,

L_(Xh-21) (h=1 to 897) is based on Structure 21,

L_(Xh-22) (h=1 to 897) is based on Structure 22,

L_(Xh-23) (h=1 to 897) is based on Structure 23,

L_(Xh-24) (h=1 to 897) is based on Structure 24,

L_(Xh-25) (h=1 to 897) is based on Structure 25,

L_(Xh-26) (h=1 to 897) is based on Structure 26,

L_(Xh-27) (h=1 to 897) is based on Structure 27,

L_(Xh-28) (h=1 to 897) is based on Structure 28,

L_(Xh-29) (h=1 to 897) is based on Structure 29,

L_(Xh-30) (h=1 to 897) is based on Structure 30,

L_(Xh-31) (h=1 to 897) is based on Structure 31,

L_(Xh-32) (h=1 to 897) is based on Structure 32,

L_(Xh-33) (h=1 to 897) is based on Structure 33,

L_(Xh-34) (h=1 to 897) is based on Structure 34,

L_(Xh-35) (h=1 to 897) is based on Structure 35,

L_(Xh-36) (h=1 to 897) is based on Structure 36,

L_(Xh-37) (h=1 to 897) is based on Structure 37,

L_(Xh-38) (h=1 to 897) is based on Structure 38,

wherein for each h, R^(E), R^(F), and Y are defined as below: h R^(E) R^(F) 1 R¹ R¹ 2 R¹ R² 3 R¹ R³ 4 R¹ R⁴ 5 R¹ R⁵ 6 R¹ R⁶ 7 R¹ R⁷ 8 R¹ R⁸ 9 R¹ R⁹ 10 R¹ R¹⁰ 11 R¹ R¹¹ 12 R¹ R¹² 13 R¹ R¹³ 14 R¹ R¹⁴ 15 R¹ R¹⁵ 16 R¹ R¹⁶ 17 R¹ R¹⁷ 18 R¹ R¹⁸ 19 R¹ R¹⁹ 20 R¹ R²⁰ 21 R¹ R²¹ 22 R¹ R²² 23 R¹ R²³ 24 R¹ R²⁴ 25 R¹ R²⁵ 26 R¹ R²⁶ 27 R¹ R²⁷ 28 R¹ R²⁸ 29 R¹ R²⁹ 30 R¹ R³⁰ 31 R¹ R³¹ 32 R¹ R³² 33 R¹ R³³ 34 R¹ R³⁴ 35 R¹ R³⁵ 36 R¹ R³⁶ 37 R¹ R³⁷ 38 R¹ R³⁸ 39 R¹ R³⁹ 40 R¹ R⁴⁰ 41 R¹ R⁴¹ 42 R¹ R⁴² 43 R¹ R⁴³ 44 R¹ R⁴⁴ 45 R¹ R⁴⁵ 46 R¹ R⁴⁶ 47 R¹ R⁴⁷ 48 R¹ R⁴⁸ 49 R¹ R⁴⁹ 50 R¹ R⁵⁰ 51 R¹ R⁵¹ 52 R¹ R⁵² 53 R¹ R⁵³ 54 R¹ R⁵⁴ 55 R¹ R⁵⁵ 56 R¹ R⁵⁶ 57 R¹ R⁵⁷ 58 R¹ R⁵⁸ 59 R¹ R⁵⁹ 60 R¹ R⁶⁰ 61 R¹ R⁶¹ 62 R¹ R⁶² 63 R¹ R⁶³ 64 R¹ R⁶⁴ 65 R¹ R⁶⁵ 66 R¹ R⁶⁶ 67 R¹ R⁶⁷ 68 R¹ R⁶⁸ 69 R¹ R⁶⁹ 70 R² R¹ 71 R² R² 72 R² R³ 73 R² R⁴ 74 R² R⁵ 75 R² R⁶ 76 R² R⁷ 77 R² R⁸ 78 R² R⁹ 79 R² R¹⁰ 80 R² R¹¹ 81 R² R¹² 82 R² R¹³ 83 R² R¹⁴ 84 R² R¹⁵ 85 R² R¹⁶ 86 R² R¹⁷ 87 R² R¹⁸ 88 R² R¹⁹ 89 R² R²⁰ 90 R² R²¹ 91 R² R²² 92 R² R²³ 93 R² R²⁴ 94 R² R²⁵ 95 R² R²⁶ 96 R² R²⁷ 97 R² R²⁸ 98 R² R²⁹ 99 R² R³⁰ 100 R² R³¹ 101 R² R³² 102 R² R³³ 103 R² R³⁴ 104 R² R³⁵ 105 R² R³⁶ 106 R² R³⁷ 107 R² R³⁸ 108 R² R³⁹ 109 R² R⁴⁰ 110 R² R⁴¹ 111 R² R⁴² 112 R² R⁴³ 113 R² R⁴⁴ 114 R² R⁴⁵ 115 R² R⁴⁶ 116 R² R⁴⁷ 117 R² R⁴⁸ 118 R² R⁴⁹ 119 R² R⁵⁰ 120 R² R⁵¹ 121 R² R⁵² 122 R² R⁵³ 123 R² R⁵⁴ 124 R² R⁵⁵ 125 R² R⁵⁶ 126 R² R⁵⁷ 127 R² R⁵⁸ 128 R² R⁵⁹ 129 R² R⁶⁰ 130 R² R⁶¹ 131 R² R⁶² 132 R² R⁶³ 133 R² R⁶⁴ 134 R² R⁶⁵ 135 R² R⁶⁶ 136 R² R⁶⁷ 137 R² R⁶⁸ 138 R² R⁶⁹ 139 R³ R¹ 140 R³ R² 141 R³ R³ 142 R³ R⁴ 143 R³ R⁵ 144 R³ R⁶ 145 R³ R⁷ 146 R³ R⁸ 147 R³ R⁹ 148 R³ R¹⁰ 149 R³ R¹¹ 150 R³ R¹² 151 R³ R¹³ 152 R³ R¹⁴ 153 R³ R¹⁵ 154 R³ R¹⁶ 155 R³ R¹⁷ 156 R³ R¹⁸ 157 R³ R¹⁹ 158 R³ R²⁰ 159 R³ R²¹ 160 R³ R²² 161 R³ R²³ 162 R³ R²⁴ 163 R³ R²⁵ 164 R³ R²⁶ 165 R³ R²⁷ 166 R³ R²⁸ 167 R³ R²⁹ 168 R³ R³⁰ 169 R³ R³¹ 170 R³ R³² 171 R³ R³³ 172 R³ R³⁴ 173 R³ R³⁵ 174 R³ R³⁶ 175 R³ R³⁷ 176 R³ R³⁸ 177 R³ R³⁹ 178 R³ R⁴⁰ 179 R³ R⁴¹ 180 R³ R⁴² 181 R³ R⁴³ 182 R³ R⁴⁴ 183 R³ R⁴⁵ 184 R³ R⁴⁶ 185 R³ R⁴⁷ 186 R³ R⁴⁸ 187 R³ R⁴⁹ 188 R³ R⁵⁰ 189 R³ R⁵¹ 190 R³ R⁵² 191 R³ R⁵³ 192 R³ R⁵⁴ 193 R³ R⁵⁵ 194 R³ R⁵⁶ 195 R³ R⁵⁷ 196 R³ R⁵⁸ 197 R³ R⁵⁹ 198 R³ R⁶⁰ 199 R³ R⁶¹ 200 R³ R⁶² 201 R³ R⁶³ 202 R³ R⁶⁴ 203 R³ R⁶⁵ 204 R³ R⁶⁶ 205 R³ R⁶⁷ 206 R³ R⁶⁸ 207 R³ R⁶⁹ 208 R⁴ R¹ 209 R⁴ R² 210 R⁴ R³ 211 R⁴ R⁴ 212 R⁴ R⁵ 213 R⁴ R⁶ 214 R⁴ R⁷ 215 R⁴ R⁸ 216 R⁴ R⁹ 217 R⁴ R¹⁰ 218 R⁴ R¹¹ 219 R⁴ R¹² 220 R⁴ R¹³ 221 R⁴ R¹⁴ 222 R⁴ R¹⁵ 223 R⁴ R¹⁶ 224 R⁴ R¹⁷ 225 R⁴ R¹⁸ 226 R⁴ R¹⁹ 227 R⁴ R²⁰ 228 R⁴ R²¹ 229 R⁴ R²² 230 R⁴ R²³ 231 R⁴ R²⁴ 232 R⁴ R²⁵ 233 R⁴ R²⁶ 234 R⁴ R²⁷ 235 R⁴ R²⁸ 236 R⁴ R²⁹ 237 R⁴ R³⁰ 238 R⁴ R³¹ 239 R⁴ R³² 240 R⁴ R³³ 241 R⁴ R³⁴ 242 R⁴ R³⁵ 243 R⁴ R³⁶ 244 R⁴ R³⁷ 245 R⁴ R³⁸ 246 R⁴ R³⁹ 247 R⁴ R⁴⁰ 248 R⁴ R⁴¹ 249 R⁴ R⁴² 250 R⁴ R⁴³ 251 R⁴ R⁴⁴ 252 R⁴ R⁴⁵ 253 R⁴ R⁴⁶ 254 R⁴ R⁴⁷ 255 R⁴ R⁴⁸ 256 R⁴ R⁴⁹ 257 R⁴ R⁵⁰ 258 R⁴ R⁵¹ 259 R⁴ R⁵² 260 R⁴ R⁵³ 261 R⁴ R⁵⁴ 262 R⁴ R⁵⁵ 263 R⁴ R⁵⁶ 264 R⁴ R⁵⁷ 265 R⁴ R⁵⁸ 266 R⁴ R⁵⁹ 267 R⁴ R⁶⁰ 268 R⁴ R⁶¹ 269 R⁴ R⁶² 270 R⁴ R⁶³ 271 R⁴ R⁶⁴ 272 R⁴ R⁶⁵ 273 R⁴ R⁶⁶ 274 R⁴ R⁶⁷ 275 R⁴ R⁶⁸ 276 R⁴ R⁶⁹ 277 R⁵ R¹ 278 R⁵ R² 279 R⁵ R³ 280 R⁵ R⁴ 281 R⁵ R⁵ 282 R⁵ R⁶ 283 R⁵ R⁷ 284 R⁵ R⁸ 285 R⁵ R⁹ 286 R⁵ R¹⁰ 287 R⁵ R¹¹ 288 R⁵ R¹² 289 R⁵ R¹³ 290 R⁵ R¹⁴ 291 R⁵ R¹⁵ 292 R⁵ R¹⁶ 293 R⁵ R¹⁷ 294 R⁵ R¹⁸ 295 R⁵ R¹⁹ 296 R⁵ R²⁰ 297 R⁵ R²¹ 298 R⁵ R²² 299 R⁵ R²³ 300 R⁵ R²⁴ 301 R⁵ R²⁵ 302 R⁵ R²⁶ 303 R⁵ R²⁷ 304 R⁵ R²⁸ 305 R⁵ R²⁹ 306 R⁵ R³⁰ 307 R⁵ R³¹ 308 R⁵ R³² 309 R⁵ R³³ 310 R⁵ R³⁴ 311 R⁵ R³⁵ 312 R⁵ R³⁶ 313 R⁵ R³⁷ 314 R⁵ R³⁸ 315 R⁵ R³⁹ 316 R⁵ R⁴⁰ 317 R⁵ R⁴¹ 318 R⁵ R⁴² 319 R⁵ R⁴³ 320 R⁵ R⁴⁴ 321 R⁵ R⁴⁵ 322 R⁵ R⁴⁶ 323 R⁵ R⁴⁷ 324 R⁵ R⁴⁸ 325 R⁵ R⁴⁹ 326 R⁵ R⁵⁰ 327 R⁵ R⁵¹ 328 R⁵ R⁵² 329 R⁵ R⁵³ 330 R⁵ R⁵⁴ 331 R⁵ R⁵⁵ 332 R⁵ R⁵⁶ 333 R⁵ R⁵⁷ 334 R⁵ R⁵⁸ 335 R⁵ R⁵⁹ 336 R⁵ R⁶⁰ 337 R⁵ R⁶¹ 338 R⁵ R⁶² 339 R⁵ R⁶³ 340 R⁵ R⁶⁴ 341 R⁵ R⁶⁵ 342 R⁵ R⁶⁶ 343 R⁵ R⁶⁷ 344 R⁵ R⁶⁸ 345 R⁵ R⁶⁹ 346 R⁶ R¹ 347 R⁶ R² 348 R⁶ R³ 349 R⁶ R⁴ 350 R⁶ R⁵ 351 R⁶ R⁶ 352 R⁶ R⁷ 353 R⁶ R⁸ 354 R⁶ R⁹ 355 R⁶ R¹⁰ 356 R⁶ R¹¹ 357 R⁶ R¹² 358 R⁶ R¹³ 359 R⁶ R¹⁴ 360 R⁶ R¹⁵ 361 R⁶ R¹⁶ 362 R⁶ R¹⁷ 363 R⁶ R¹⁸ 364 R⁶ R¹⁹ 365 R⁶ R²⁰ 366 R⁶ R²¹ 367 R⁶ R²² 368 R⁶ R²³ 369 R⁶ R²⁴ 370 R⁶ R²⁵ 371 R⁶ R²⁶ 372 R⁶ R²⁷ 373 R⁶ R²⁸ 374 R⁶ R²⁹ 375 R⁶ R³⁰ 376 R⁶ R³¹ 377 R⁶ R³² 378 R⁶ R³³ 379 R⁶ R³⁴ 380 R⁶ R³⁵ 381 R⁶ R³⁶ 382 R⁶ R³⁷ 383 R⁶ R³⁸ 384 R⁶ R³⁹ 385 R⁶ R⁴⁰ 386 R⁶ R⁴¹ 387 R⁶ R⁴² 388 R⁶ R⁴³ 389 R⁶ R⁴⁴ 390 R⁶ R⁴⁵ 391 R⁶ R⁴⁶ 392 R⁶ R⁴⁷ 393 R⁶ R⁴⁸ 394 R⁶ R⁴⁹ 395 R⁶ R⁵⁰ 396 R⁶ R⁵¹ 397 R⁶ R⁵² 398 R⁶ R⁵³ 399 R⁶ R⁵⁴ 400 R⁶ R⁵⁵ 401 R⁶ R⁵⁶ 402 R⁶ R⁵⁷ 403 R⁶ R⁵⁸ 404 R⁶ R⁵⁹ 405 R⁶ R⁶⁰ 406 R⁶ R⁶¹ 407 R⁶ R⁶² 408 R⁶ R⁶³ 409 R⁶ R⁶⁴ 410 R⁶ R⁶⁵ 411 R⁶ R⁶⁶ 412 R⁶ R⁶⁷ 413 R⁶ R⁶⁸ 414 R⁶ R⁶⁹ 415 R⁷ R¹ 416 R⁷ R² 417 R⁷ R³ 418 R⁷ R⁴ 419 R⁷ R⁵ 420 R⁷ R⁶ 421 R⁷ R⁷ 422 R⁷ R⁸ 423 R⁷ R⁹ 424 R⁷ R¹⁰ 425 R⁷ R¹¹ 426 R⁷ R¹² 427 R⁷ R¹³ 428 R⁷ R¹⁴ 429 R⁷ R¹⁵ 430 R⁷ R¹⁶ 431 R⁷ R¹⁷ 432 R⁷ R¹⁸ 433 R⁷ R¹⁹ 434 R⁷ R²⁰ 435 R⁷ R²¹ 436 R⁷ R²² 437 R⁷ R²³ 438 R⁷ R²⁴ 439 R⁷ R²⁵ 440 R⁷ R²⁶ 441 R⁷ R²⁷ 442 R⁷ R²⁸ 443 R⁷ R²⁹ 444 R⁷ R³⁰ 445 R⁷ R³¹ 446 R⁷ R³² 447 R⁷ R³³ 448 R⁷ R³⁴ 449 R⁷ R³⁵ 450 R⁷ R³⁶ 451 R⁷ R³⁷ 452 R⁷ R³⁸ 453 R⁷ R³⁹ 454 R⁷ R⁴⁰ 455 R⁷ R⁴¹ 456 R⁷ R⁴² 457 R⁷ R⁴³ 458 R⁷ R⁴⁴ 459 R⁷ R⁴⁵ 460 R⁷ R⁴⁶ 461 R⁷ R⁴⁷ 462 R⁷ R⁴⁸ 463 R⁷ R⁴⁹ 464 R⁷ R⁵⁰ 465 R⁷ R⁵¹ 466 R⁷ R⁵² 467 R⁷ R⁵³ 468 R⁷ R⁵⁴ 469 R⁷ R⁵⁵ 470 R⁷ R⁵⁶ 471 R⁷ R⁵⁷ 472 R⁷ R⁵⁸ 473 R⁷ R⁵⁹ 474 R⁷ R⁶⁰ 475 R⁷ R⁶¹ 476 R⁷ R⁶² 477 R⁷ R⁶³ 478 R⁷ R⁶⁴ 479 R⁷ R⁶⁵ 480 R⁷ R⁶⁶ 481 R⁷ R⁶⁷ 482 R⁷ R⁶⁸ 483 R⁷ R⁶⁹ 484 R³⁰ R¹ 485 R³⁰ R² 486 R³⁰ R³ 487 R³⁰ R⁴ 488 R³⁰ R⁵ 489 R³⁰ R⁶ 490 R³⁰ R⁷ 491 R³⁰ R⁸ 492 R³⁰ R⁹ 493 R³⁰ R¹⁰ 494 R³⁰ R¹¹ 495 R³⁰ R¹² 496 R³⁰ R¹³ 497 R³⁰ R¹⁴ 498 R³⁰ R¹⁵ 499 R³⁰ R¹⁶ 500 R³⁰ R¹⁷ 501 R³⁰ R¹⁸ 502 R³⁰ R¹⁹ 503 R³⁰ R²⁰ 504 R³⁰ R²¹ 505 R³⁰ R²² 506 R³⁰ R²³ 507 R³⁰ R²⁴ 508 R³⁰ R²⁵ 509 R³⁰ R²⁶ 510 R³⁰ R²⁷ 511 R³⁰ R²⁸ 512 R³⁰ R²⁹ 513 R³⁰ R³⁰ 514 R³⁰ R³¹ 515 R³⁰ R³² 516 R³⁰ R³³ 517 R³⁰ R³⁴ 518 R³⁰ R³⁵ 519 R³⁰ R³⁶ 520 R³⁰ R³⁷ 521 R³⁰ R³⁸ 522 R³⁰ R³⁹ 523 R³⁰ R⁴⁰ 524 R³⁰ R⁴¹ 525 R³⁰ R⁴² 526 R³⁰ R⁴³ 527 R³⁰ R⁴⁴ 528 R³⁰ R⁴⁵ 529 R³⁰ R⁴⁶ 530 R³⁰ R⁴⁷ 531 R³⁰ R⁴⁸ 532 R³⁰ R⁴⁹ 533 R³⁰ R⁵⁰ 534 R³⁰ R⁵¹ 535 R³⁰ R⁵² 536 R³⁰ R⁵³ 537 R³⁰ R⁵⁴ 538 R³⁰ R⁵⁵ 539 R³⁰ R⁵⁶ 540 R³⁰ R⁵⁷ 541 R³⁰ R⁵⁸ 542 R³⁰ R⁵⁹ 543 R³⁰ R⁶⁰ 544 R³⁰ R⁶¹ 545 R³⁰ R⁶² 546 R³⁰ R⁶³ 547 R³⁰ R⁶⁴ 548 R³⁰ R⁶⁵ 549 R³⁰ R⁶⁶ 550 R³⁰ R⁶⁷ 551 R³⁰ R⁶⁸ 552 R³⁰ R⁶⁹ 553 R³² R¹ 554 R³² R² 555 R³² R³ 556 R³² R⁴ 557 R³² R⁵ 558 R³² R⁶ 559 R³² R⁷ 560 R³² R⁸ 561 R³² R⁹ 562 R³² R¹⁰ 563 R³² R¹¹ 564 R³² R¹² 565 R³² R¹³ 566 R³² R¹⁴ 567 R³² R¹⁵ 568 R³² R¹⁶ 569 R³² R¹⁷ 570 R³² R¹⁸ 571 R³² R¹⁹ 572 R³² R²⁰ 573 R³² R²¹ 574 R³² R²² 575 R³² R²³ 576 R³² R²⁴ 577 R³² R²⁵ 578 R³² R²⁶ 579 R³² R²⁷ 580 R³² R²⁸ 581 R³² R²⁹ 582 R³² R³⁰ 583 R³² R³¹ 584 R³² R³² 585 R³² R³³ 586 R³² R³⁴ 587 R³² R³⁵ 588 R³² R³⁶ 589 R³² R³⁷ 590 R³² R³⁸ 591 R³² R³⁹ 592 R³² R⁴⁰ 593 R³² R⁴¹ 594 R³² R⁴² 595 R³² R⁴³ 596 R³² R⁴⁴ 597 R³² R⁴⁵ 598 R³² R⁴⁶ 599 R³² R⁴⁷ 600 R³² R⁴⁸ 601 R³² R⁴⁹ 602 R³² R⁵⁰ 603 R³² R⁵¹ 604 R³² R⁵² 605 R³² R⁵³ 606 R³² R⁵⁴ 607 R³² R⁵⁵ 608 R³² R⁵⁶ 609 R³² R⁵⁷ 610 R³² R⁵⁸ 611 R³² R⁵⁹ 612 R³² R⁶⁰ 613 R³² R⁶¹ 614 R³² R⁶² 615 R³² R⁶³ 616 R³² R⁶⁴ 617 R³² R⁶⁵ 618 R³² R⁶⁶ 619 R³² R⁶⁷ 620 R³² R⁶⁸ 621 R³² R⁶⁹ 622 R³³ R¹ 623 R³³ R² 624 R³³ R³ 625 R³³ R⁴ 626 R³³ R⁵ 627 R³³ R⁶ 628 R³³ R⁷ 629 R³³ R⁸ 630 R³³ R⁹ 631 R³³ R¹⁰ 632 R³³ R¹¹ 633 R³³ R¹² 634 R³³ R¹³ 635 R³³ R¹⁴ 636 R³³ R¹⁵ 637 R³³ R¹⁶ 638 R³³ R¹⁷ 639 R³³ R¹⁸ 640 R³³ R¹⁹ 641 R³³ R²⁰ 642 R³³ R²¹ 643 R³³ R²² 644 R³³ R²³ 645 R³³ R²⁴ 646 R³³ R²⁵ 647 R³³ R²⁶ 648 R³³ R²⁷ 649 R³³ R²⁸ 650 R³³ R²⁹ 651 R³³ R³⁰ 652 R³³ R³¹ 653 R³³ R³² 654 R³³ R³³ 655 R³³ R³⁴ 656 R³³ R³⁵ 657 R³³ R³⁶ 658 R³³ R³⁷ 659 R³³ R³⁸ 660 R³³ R³⁹ 661 R³³ R⁴⁰ 662 R³³ R⁴¹ 663 R³³ R⁴² 664 R³³ R⁴³ 665 R³³ R⁴⁴ 666 R³³ R⁴⁵ 667 R³³ R⁴⁶ 668 R³³ R⁴⁷ 669 R³³ R⁴⁸ 670 R³³ R⁴⁹ 671 R³³ R⁵⁰ 672 R³³ R⁵¹ 673 R³³ R⁵² 674 R³³ R⁵³ 675 R³³ R⁵⁴ 676 R³³ R⁵⁵ 677 R³³ R⁵⁶ 678 R³³ R⁵⁷ 679 R³³ R⁵⁸ 680 R³³ R⁵⁹ 681 R³³ R⁶⁰ 682 R³³ R⁶¹ 683 R³³ R⁶² 684 R³³ R⁶³ 685 R³³ R⁶⁴ 686 R³³ R⁶⁵ 687 R³³ R⁶⁶ 688 R³³ R⁶⁷ 689 R³³ R⁶⁸ 690 R³³ R⁶⁹ 691 R³⁴ R¹ 692 R³⁴ R² 693 R³⁴ R³ 694 R³⁴ R⁴ 695 R³⁴ R⁵ 696 R³⁴ R⁶ 697 R³⁴ R⁷ 698 R³⁴ R⁸ 699 R³⁴ R⁹ 700 R³⁴ R¹⁰ 701 R³⁴ R¹¹ 702 R³⁴ R¹² 703 R³⁴ R¹³ 704 R³⁴ R¹⁴ 705 R³⁴ R¹⁵ 706 R³⁴ R¹⁶ 707 R³⁴ R¹⁷ 708 R³⁴ R¹⁸ 709 R³⁴ R¹⁹ 710 R³⁴ R²⁰ 711 R³⁴ R²¹ 712 R³⁴ R²² 713 R³⁴ R²³ 714 R³⁴ R²⁴ 715 R³⁴ R²⁵ 716 R³⁴ R²⁶ 717 R³⁴ R²⁷ 718 R³⁴ R²⁸ 719 R³⁴ R²⁹ 720 R³⁴ R³⁰ 721 R³⁴ R³¹ 722 R³⁴ R³² 723 R³⁴ R³³ 724 R³⁴ R³⁴ 725 R³⁴ R³⁵ 726 R³⁴ R³⁶ 727 R³⁴ R³⁷ 728 R³⁴ R³⁸ 729 R³⁴ R³⁹ 730 R³⁴ R⁴⁰ 731 R³⁴ R⁴¹ 732 R³⁴ R⁴² 733 R³⁴ R⁴³ 734 R³⁴ R⁴⁴ 735 R³⁴ R⁴⁵ 736 R³⁴ R⁴⁶ 737 R³⁴ R⁴⁷ 738 R³⁴ R⁴⁸ 739 R³⁴ R⁴⁹ 740 R³⁴ R⁵⁰ 741 R³⁴ R⁵¹ 742 R³⁴ R⁵² 743 R³⁴ R⁵³ 744 R³⁴ R⁵⁴ 745 R³⁴ R⁵⁵ 746 R³⁴ R⁵⁶ 747 R³⁴ R⁵⁷ 748 R³⁴ R⁵⁸ 749 R³⁴ R⁵⁹ 750 R³⁴ R⁶⁰ 751 R³⁴ R⁶¹ 752 R³⁴ R⁶² 753 R³⁴ R⁶³ 754 R³⁴ R⁶⁴ 755 R³⁴ R⁶⁵ 756 R³⁴ R⁶⁶ 757 R³⁴ R⁶⁷ 758 R³⁴ R⁶⁸ 759 R³⁴ R⁶⁹ 760 R³⁵ R¹ 761 R³⁵ R² 762 R³⁵ R³ 763 R³⁵ R⁴ 764 R³⁵ R⁵ 765 R³⁵ R⁶ 766 R³⁵ R⁷ 767 R³⁵ R⁸ 768 R³⁵ R⁹ 769 R³⁵ R¹⁰ 770 R³⁵ R¹¹ 771 R³⁵ R¹² 772 R³⁵ R¹³ 773 R³⁵ R¹⁴ 774 R³⁵ R¹⁵ 775 R³⁵ R¹⁶ 776 R³⁵ R¹⁷ 777 R³⁵ R¹⁸ 778 R³⁵ R¹⁹ 779 R³⁵ R²⁰ 780 R³⁵ R²¹ 781 R³⁵ R²² 782 R³⁵ R²³ 783 R³⁵ R²⁴ 784 R³⁵ R²⁵ 785 R³⁵ R²⁶ 786 R³⁵ R²⁷ 787 R³⁵ R²⁸ 788 R³⁵ R²⁹ 789 R³⁵ R³⁰ 790 R³⁵ R³¹ 791 R³⁵ R³² 792 R³⁵ R³³ 793 R³⁵ R³⁴ 794 R³⁵ R³⁵ 795 R³⁵ R³⁶ 796 R³⁵ R³⁷ 797 R³⁵ R³⁸ 798 R³⁵ R³⁹ 799 R³⁵ R⁴⁰ 800 R³⁵ R⁴¹ 801 R³⁵ R⁴² 802 R³⁵ R⁴³ 803 R³⁵ R⁴⁴ 804 R³⁵ R⁴⁵ 805 R³⁵ R⁴⁶ 806 R³⁵ R⁴⁷ 807 R³⁵ R⁴⁸ 808 R³⁵ R⁴⁹ 809 R³⁵ R⁵⁰ 810 R³⁵ R⁵¹ 811 R³⁵ R⁵² 812 R³⁵ R⁵³ 813 R³⁵ R⁵⁴ 814 R³⁵ R⁵⁵ 815 R³⁵ R⁵⁶ 816 R³⁵ R⁵⁷ 817 R³⁵ R⁵⁸ 818 R³⁵ R⁵⁹ 819 R³⁵ R⁶⁰ 820 R³⁵ R⁶¹ 821 R³⁵ R⁶² 822 R³⁵ R⁶³ 823 R³⁵ R⁶⁴ 824 R³⁵ R⁶⁵ 825 R³⁵ R⁶⁶ 826 R³⁵ R⁶⁷ 827 R³⁵ R⁶⁸ 828 R³⁵ R⁶⁹ 829 R³⁶ R¹ 830 R³⁶ R² 831 R³⁶ R³ 832 R³⁶ R⁴ 833 R³⁶ R⁵ 834 R³⁶ R⁶ 835 R³⁶ R⁷ 836 R³⁶ R⁸ 837 R³⁶ R⁹ 838 R³⁶ R¹⁰ 839 R³⁶ R¹¹ 840 R³⁶ R¹² 841 R³⁶ R¹³ 842 R³⁶ R¹⁴ 843 R³⁶ R¹⁵ 844 R³⁶ R¹⁶ 845 R³⁶ R¹⁷ 846 R³⁶ R¹⁸ 847 R³⁶ R¹⁹ 848 R³⁶ R²⁰ 849 R³⁶ R²¹ 850 R³⁶ R²² 851 R³⁶ R²³ 852 R³⁶ R²⁴ 853 R³⁶ R²⁵ 854 R³⁶ R²⁶ 855 R³⁶ R²⁷ 856 R³⁶ R²⁸ 857 R³⁶ R²⁹ 858 R³⁶ R³⁰ 859 R³⁶ R³¹ 860 R³⁶ R³² 861 R³⁶ R³³ 862 R³⁶ R³⁴ 863 R³⁶ R³⁵ 864 R³⁶ R³⁶ 865 R³⁶ R³⁷ 866 R³⁶ R³⁸ 867 R³⁶ R³⁹ 868 R³⁶ R⁴⁰ 869 R³⁶ R⁴¹ 870 R³⁶ R⁴² 871 R³⁶ R⁴³ 872 R³⁶ R⁴⁴ 873 R³⁶ R⁴⁵ 874 R³⁶ R⁴⁶ 875 R³⁶ R⁴⁷ 876 R³⁶ R⁴⁸ 877 R³⁶ R⁴⁹ 878 R³⁶ R⁵⁰ 879 R³⁶ R⁵¹ 880 R³⁶ R⁵² 881 R³⁶ R⁵³ 882 R³⁶ R⁵⁴ 883 R³⁶ R⁵⁵ 884 R³⁶ R⁵⁶ 885 R³⁶ R⁵⁷ 886 R³⁶ R⁵⁸ 887 R³⁶ R⁵⁹ 888 R³⁶ R⁶⁰ 889 R³⁶ R⁶¹ 890 R³⁶ R⁶² 891 R³⁶ R⁶³ 892 R³⁶ R⁶⁴ 893 R³⁶ R⁶⁵ 894 R³⁶ R⁶⁶ 895 R³⁶ R⁶⁷ 896 R³⁶ R⁶⁸ 897 R³⁶ R⁶⁹

wherein for each L_(Xi-n); L_(Xi-39) (i=1 to 1446) are based on Structure 39,

L_(Xi-40) (h=1 to 1446) is based on Structure 40,

L_(Xi-41) (h=1 to 1446) is based on Structure 41,

L_(Xi-42) (h=1 to 1446) is based on Structure 42,

L_(Xi-43) (h=1 to 1446) is based on Structure 43,

L_(Xi-44) (h=1 to 1446) is based on Structure 44,

L_(Xi-45) (h=1 to 1446) is based on Structure 45,

L_(Xi-46) (h=1 to 1446) is based on Structure 46,

L_(Xi-47) (h=1 to 1446) is based on Structure 47,

L_(Xi-48) (h=1 to 1446) is based on Structure 48,

L_(Xi-49) (h=1 to 1446) is based on Structure 49,

L_(Xi-50) (h=1 to 1446) is based on Structure 50,

L_(Xi-51) (h=1 to 1446) is based on Structure 51,

L_(Xi-52) (h=1 to 1446) is based on Structure 52,

L_(Xi-53) (h=1 to 1446) is based on Structure 53,

L_(Xi-54) (h=1 to 1446) is based on Structure 54,

L_(Xi-55) (h=1 to 1446) is based on Structure 55,

L_(Xi-56) (h=1 to 1446) is based on Structure 56,

L_(Xi-57) (h=1 to 1446) is based on Structure 57,

wherein for each i, R^(E), R^(F), and R^(G) are defined as below: i R^(E) R^(F) R^(G) 1 R¹ R¹ R¹ 2 R¹ R¹ R² 3 R¹ R¹ R³ 4 R¹ R¹ R⁴ 5 R¹ R¹ R⁵ 6 R¹ R¹ R⁶ 7 R¹ R¹ R⁷ 8 R¹ R¹ R⁸ 9 R¹ R¹ R⁹ 10 R¹ R¹ R¹⁰ 11 R¹ R¹ R¹¹ 12 R¹ R¹ R¹² 13 R¹ R¹ R¹³ 14 R¹ R¹ R¹⁴ 15 R¹ R¹ R¹⁵ 16 R¹ R¹ R¹⁶ 17 R¹ R¹ R¹⁷ 18 R¹ R¹ R¹⁸ 19 R¹ R¹ R¹⁹ 20 R¹ R¹ R²⁰ 21 R¹ R¹ R²¹ 22 R¹ R¹ R²² 23 R¹ R¹ R²³ 24 R¹ R¹ R²⁴ 25 R¹ R¹ R²⁵ 26 R¹ R¹ R²⁶ 27 R¹ R¹ R²⁷ 28 R¹ R¹ R²⁸ 29 R¹ R¹ R²⁹ 30 R¹ R¹ R³⁰ 31 R¹ R¹ R³¹ 32 R¹ R¹ R³² 33 R¹ R¹ R³³ 34 R¹ R¹ R³⁴ 35 R¹ R¹ R³⁵ 36 R¹ R¹ R³⁶ 37 R¹ R¹ R³⁷ 38 R¹ R¹ R³⁸ 39 R¹ R¹ R³⁹ 40 R¹ R¹ R⁴⁰ 41 R¹ R¹ R⁴¹ 42 R¹ R¹ R⁴² 43 R¹ R¹ R⁴³ 44 R¹ R¹ R⁴⁴ 45 R¹ R¹ R⁴⁵ 46 R¹ R¹ R⁴⁶ 47 R¹ R¹ R⁴⁷ 48 R¹ R¹ R⁴⁸ 49 R¹ R¹ R⁴⁹ 50 R¹ R¹ R⁵⁰ 51 R¹ R¹ R⁵¹ 52 R¹ R¹ R⁵² 53 R¹ R¹ R⁵³ 54 R¹ R¹ R⁵⁴ 55 R¹ R¹ R⁵⁵ 56 R¹ R¹ R⁵⁶ 57 R¹ R¹ R⁵⁷ 58 R¹ R¹ R⁵⁸ 59 R¹ R¹ R⁵⁹ 60 R¹ R¹ R⁶⁰ 61 R¹ R¹ R⁶¹ 62 R¹ R¹ R⁶² 63 R¹ R¹ R⁶³ 64 R¹ R¹ R⁶⁴ 65 R¹ R¹ R⁶⁵ 66 R¹ R¹ R⁶⁶ 67 R¹ R¹ R⁶⁷ 68 R¹ R¹ R⁶⁸ 69 R¹ R¹ R⁶⁹ 70 R¹ R² R¹ 71 R¹ R² R² 72 R¹ R² R³ 73 R¹ R² R⁴ 74 R¹ R² R⁵ 75 R¹ R² R⁶ 76 R¹ R² R⁷ 77 R¹ R² R⁸ 78 R¹ R² R⁹ 79 R¹ R² R¹⁰ 80 R¹ R² R¹¹ 81 R¹ R² R¹² 82 R¹ R² R¹³ 83 R¹ R² R¹⁴ 84 R¹ R² R¹⁵ 85 R¹ R² R¹⁶ 86 R¹ R² R¹⁷ 87 R¹ R² R¹⁸ 88 R¹ R² R¹⁹ 89 R¹ R² R²⁰ 90 R¹ R² R²¹ 91 R¹ R² R²² 92 R¹ R² R²³ 93 R¹ R² R²⁴ 94 R¹ R² R²⁵ 95 R¹ R² R²⁶ 96 R¹ R² R²⁷ 97 R¹ R² R²⁸ 98 R¹ R² R²⁹ 99 R¹ R² R³⁰ 100 R¹ R² R³¹ 101 R¹ R² R³² 102 R¹ R² R³³ 103 R¹ R² R³⁴ 104 R¹ R² R³⁵ 105 R¹ R² R³⁶ 106 R¹ R² R³⁷ 107 R¹ R² R³⁸ 108 R¹ R² R³⁹ 109 R¹ R² R⁴⁰ 110 R¹ R² R⁴¹ 111 R¹ R² R⁴² 112 R¹ R² R⁴³ 113 R¹ R² R⁴⁴ 114 R¹ R² R⁴⁵ 115 R¹ R² R⁴⁶ 116 R¹ R² R⁴⁷ 117 R¹ R² R⁴⁸ 118 R¹ R² R⁴⁹ 119 R¹ R² R⁵⁰ 120 R¹ R² R⁵¹ 121 R¹ R² R⁵² 122 R¹ R² R⁵³ 123 R¹ R² R⁵⁴ 124 R¹ R² R⁵⁵ 125 R¹ R² R⁵⁶ 126 R¹ R² R⁵⁷ 127 R¹ R² R⁵⁸ 128 R¹ R² R⁵⁹ 129 R¹ R² R⁶⁰ 130 R¹ R² R⁶¹ 131 R¹ R² R⁶² 132 R¹ R² R⁶³ 133 R¹ R² R⁶⁴ 134 R¹ R² R⁶⁵ 135 R¹ R² R⁶⁶ 136 R¹ R² R⁶⁷ 137 R¹ R² R⁶⁸ 138 R¹ R² R⁶⁹ 139 R¹ R⁷ R¹ 140 R¹ R² R² 141 R¹ R³ R³ 142 R¹ R⁴ R⁴ 143 R¹ R⁵ R⁵ 144 R¹ R⁶ R⁶ 145 R¹ R⁷ R⁷ 146 R¹ R⁷ R⁸ 147 R¹ R⁷ R⁹ 148 R¹ R⁷ R¹⁰ 149 R¹ R⁷ R¹¹ 150 R¹ R⁷ R¹² 151 R¹ R⁷ R¹³ 152 R¹ R⁷ R¹⁴ 153 R¹ R⁷ R¹⁵ 154 R¹ R⁷ R¹⁶ 155 R¹ R⁷ R¹⁷ 156 R¹ R⁷ R¹⁸ 157 R¹ R⁷ R¹⁹ 158 R¹ R⁷ R²⁰ 159 R¹ R⁷ R²¹ 160 R¹ R⁷ R²² 161 R¹ R⁷ R²³ 162 R¹ R⁷ R²⁴ 163 R¹ R⁷ R²⁵ 164 R¹ R⁷ R²⁶ 165 R¹ R⁷ R²⁷ 166 R¹ R⁷ R²⁸ 167 R¹ R⁷ R²⁹ 168 R¹ R⁷ R³⁰ 169 R¹ R⁷ R³¹ 170 R¹ R⁷ R³² 171 R¹ R⁷ R³³ 172 R¹ R⁷ R³⁴ 173 R¹ R⁷ R³⁵ 174 R¹ R⁷ R³⁶ 175 R¹ R⁷ R³⁷ 176 R¹ R⁷ R³⁸ 177 R¹ R⁷ R³⁹ 178 R¹ R⁷ R⁴⁰ 179 R¹ R⁷ R⁴¹ 180 R¹ R⁷ R⁴² 181 R¹ R⁷ R⁴³ 182 R¹ R⁷ R⁴⁴ 183 R¹ R⁷ R⁴⁵ 184 R¹ R⁷ R⁴⁶ 185 R¹ R⁷ R⁴⁷ 186 R¹ R⁷ R⁴⁸ 187 R¹ R⁷ R⁴⁹ 188 R¹ R⁷ R⁵⁰ 189 R¹ R⁷ R⁵¹ 190 R¹ R⁷ R⁵² 191 R¹ R⁷ R⁵³ 192 R¹ R⁷ R⁵⁴ 193 R¹ R⁷ R⁵⁵ 194 R¹ R⁷ R⁵⁶ 195 R¹ R⁷ R⁵⁷ 196 R¹ R⁷ R⁵⁸ 197 R¹ R⁷ R⁵⁹ 198 R¹ R⁷ R⁶⁰ 199 R¹ R⁷ R⁶¹ 200 R¹ R⁷ R⁶² 201 R¹ R⁷ R⁶³ 202 R¹ R⁷ R⁶⁴ 203 R¹ R⁷ R⁶⁵ 204 R¹ R⁷ R⁶⁶ 205 R¹ R⁷ R⁶⁷ 206 R¹ R⁷ R⁶⁸ 207 R¹ R⁷ R⁶⁹ 208 R¹ R¹⁴ R¹ 209 R¹ R¹⁴ R² 210 R¹ R¹⁴ R³ 211 R¹ R¹⁴ R⁴ 212 R¹ R¹⁴ R⁵ 213 R¹ R¹⁴ R⁶ 214 R¹ R¹⁴ R⁷ 215 R¹ R¹⁴ R⁸ 216 R¹ R¹⁴ R⁹ 217 R¹ R¹⁴ R¹⁰ 218 R¹ R¹⁴ R¹¹ 219 R¹ R¹⁴ R¹² 220 R¹ R¹⁴ R¹³ 221 R¹ R¹⁴ R¹⁴ 222 R¹ R¹⁴ R¹⁵ 223 R¹ R¹⁴ R¹⁶ 224 R¹ R¹⁴ R¹⁷ 225 R¹ R¹⁴ R¹⁸ 226 R¹ R¹⁴ R¹⁹ 227 R¹ R¹⁴ R²⁰ 228 R¹ R¹⁴ R²¹ 229 R¹ R¹⁴ R²² 230 R¹ R¹⁴ R²³ 231 R¹ R¹⁴ R²⁴ 232 R¹ R¹⁴ R²⁵ 233 R¹ R¹⁴ R²⁶ 234 R¹ R¹⁴ R²⁷ 235 R¹ R¹⁴ R²⁸ 236 R¹ R¹⁴ R²⁹ 237 R¹ R¹⁴ R³⁰ 238 R¹ R¹⁴ R³¹ 239 R¹ R¹⁴ R³² 240 R¹ R¹⁴ R³³ 241 R¹ R¹⁴ R³⁴ 242 R¹ R¹⁴ R³⁵ 243 R¹ R¹⁴ R³⁶ 244 R¹ R¹⁴ R³⁷ 245 R¹ R¹⁴ R³⁸ 246 R¹ R¹⁴ R³⁹ 247 R¹ R¹⁴ R⁴⁰ 248 R¹ R¹⁴ R⁴¹ 249 R¹ R¹⁴ R⁴² 250 R¹ R¹⁴ R⁴³ 251 R¹ R¹⁴ R⁴⁴ 252 R¹ R¹⁴ R⁴⁵ 253 R¹ R¹⁴ R⁴⁶ 254 R¹ R¹⁴ R⁴⁷ 255 R¹ R¹⁴ R⁴⁸ 256 R¹ R¹⁴ R⁴⁹ 257 R¹ R¹⁴ R⁵⁰ 258 R¹ R¹⁴ R⁵¹ 259 R¹ R¹⁴ R⁵² 260 R¹ R¹⁴ R⁵³ 261 R¹ R¹⁴ R⁵⁴ 262 R¹ R¹⁴ R⁵⁵ 263 R¹ R¹⁴ R⁵⁶ 264 R¹ R¹⁴ R⁵⁷ 265 R¹ R¹⁴ R⁵⁸ 266 R¹ R¹⁴ R⁵⁹ 267 R¹ R¹⁴ R⁶⁰ 268 R¹ R¹⁴ R⁶¹ 269 R¹ R¹⁴ R⁶² 270 R¹ R¹⁴ R⁶³ 271 R¹ R¹⁴ R⁶⁴ 272 R¹ R¹⁴ R⁶⁵ 273 R¹ R¹⁴ R⁶⁶ 274 R¹ R¹⁴ R⁶⁷ 275 R¹ R¹⁴ R⁶⁸ 276 R¹ R¹⁴ R⁶⁹ 277 R¹ R³² R¹ 278 R¹ R³² R² 279 R¹ R³² R³ 280 R¹ R³² R⁴ 281 R¹ R³² R⁵ 282 R¹ R³² R⁶ 283 R¹ R³² R⁷ 284 R¹ R³² R⁸ 285 R¹ R³² R⁹ 286 R¹ R³² R¹⁰ 287 R¹ R³² R¹¹ 288 R¹ R³² R¹² 289 R¹ R³² R¹³ 290 R¹ R³² R¹⁴ 291 R¹ R³² R¹⁵ 292 R¹ R³² R¹⁶ 293 R¹ R³² R¹⁷ 294 R¹ R³² R¹⁸ 295 R¹ R³² R¹⁹ 296 R¹ R³² R²⁰ 297 R¹ R³² R²¹ 298 R¹ R³² R²² 299 R¹ R³² R²³ 300 R¹ R³² R²⁴ 301 R¹ R³² R²⁵ 302 R¹ R³² R²⁶ 303 R¹ R³² R²⁷ 304 R¹ R³² R²⁸ 305 R¹ R³² R²⁹ 306 R¹ R³² R³⁰ 307 R¹ R³² R³¹ 308 R¹ R³² R³² 309 R¹ R³² R³³ 310 R¹ R³² R³⁴ 311 R¹ R³² R³⁵ 312 R¹ R³² R³⁶ 313 R¹ R³² R³⁷ 314 R¹ R³² R³⁸ 315 R¹ R³² R³⁹ 316 R¹ R³² R⁴⁰ 317 R¹ R³² R⁴¹ 318 R¹ R³² R⁴² 319 R¹ R³² R⁴³ 320 R¹ R³² R⁴⁴ 321 R¹ R³² R⁴⁵ 322 R¹ R³² R⁴⁶ 323 R¹ R³² R⁴⁷ 324 R¹ R³² R⁴⁸ 325 R¹ R³² R⁴⁹ 326 R¹ R³² R⁵⁰ 327 R¹ R³² R⁵¹ 328 R¹ R³² R⁵² 329 R¹ R³² R⁵³ 330 R¹ R³² R⁵⁴ 331 R¹ R³² R⁵⁵ 332 R¹ R³² R⁵⁶ 333 R¹ R³² R⁵⁷ 334 R¹ R³² R⁵⁸ 335 R¹ R³² R⁵⁹ 336 R¹ R³² R⁶⁰ 337 R¹ R³² R⁶¹ 338 R¹ R³² R⁶² 339 R¹ R³² R⁶³ 340 R¹ R³² R⁶⁴ 341 R¹ R³² R⁶⁵ 342 R¹ R³² R⁶⁶ 343 R¹ R³² R⁶⁷ 344 R¹ R³² R⁶⁸ 345 R¹ R³² R⁶⁹ 346 R¹ R³⁶ R¹ 347 R¹ R³⁶ R² 348 R¹ R³⁶ R³ 349 R¹ R³⁶ R⁴ 350 R¹ R³⁶ R⁵ 351 R¹ R³⁶ R⁶ 352 R¹ R³⁶ R⁷ 353 R¹ R³⁶ R⁸ 354 R¹ R³⁶ R⁹ 355 R¹ R³⁶ R¹⁰ 356 R¹ R³⁶ R¹¹ 357 R¹ R³⁶ R¹² 358 R¹ R³⁶ R¹³ 359 R¹ R³⁶ R¹⁴ 360 R¹ R³⁶ R¹⁵ 361 R¹ R³⁶ R¹⁶ 362 R¹ R³⁶ R¹⁷ 363 R¹ R³⁶ R¹⁸ 364 R¹ R³⁶ R¹⁹ 365 R¹ R³⁶ R²⁰ 366 R¹ R³⁶ R²¹ 367 R¹ R³⁶ R²² 368 R¹ R³⁶ R²³ 369 R¹ R³⁶ R²⁴ 370 R¹ R³⁶ R²⁵ 371 R¹ R³⁶ R²⁶ 372 R¹ R³⁶ R²⁷ 373 R¹ R³⁶ R²⁸ 374 R¹ R³⁶ R²⁹ 375 R¹ R³⁶ R³⁰ 376 R¹ R³⁶ R³¹ 377 R¹ R³⁶ R³² 378 R¹ R³⁶ R³³ 379 R¹ R³⁶ R³⁴ 380 R¹ R³⁶ R³⁵ 381 R¹ R³⁶ R³⁶ 382 R¹ R³⁶ R³⁷ 383 R¹ R³⁶ R³⁸ 384 R¹ R³⁶ R³⁹ 385 R¹ R³⁶ R⁴⁰ 386 R¹ R³⁶ R⁴¹ 387 R¹ R³⁶ R⁴² 388 R¹ R³⁶ R⁴³ 389 R¹ R³⁶ R⁴⁴ 390 R¹ R³⁶ R⁴⁵ 391 R¹ R³⁶ R⁴⁶ 392 R¹ R³⁶ R⁴⁷ 393 R¹ R³⁶ R⁴⁸ 394 R¹ R³⁶ R⁴⁹ 395 R¹ R³⁶ R⁵⁰ 396 R¹ R³⁶ R⁵¹ 397 R¹ R³⁶ R⁵² 398 R¹ R³⁶ R⁵³ 399 R¹ R³⁶ R⁵⁴ 400 R¹ R³⁶ R⁵⁵ 401 R¹ R³⁶ R⁵⁶ 402 R¹ R³⁶ R⁵⁷ 403 R¹ R³⁶ R⁵⁸ 404 R¹ R³⁶ R⁵⁹ 405 R¹ R³⁶ R⁶⁰ 406 R¹ R³⁶ R⁶¹ 407 R¹ R³⁶ R⁶² 408 R¹ R³⁶ R⁶³ 409 R¹ R³⁶ R⁶⁴ 410 R¹ R³⁶ R⁶⁵ 411 R¹ R³⁶ R⁶⁶ 412 R¹ R³⁶ R⁶⁷ 413 R¹ R³⁶ R⁶⁸ 414 R¹ R³⁶ R⁶⁹ 415 R¹ R⁴¹ R¹ 416 R¹ R⁴¹ R² 417 R¹ R⁴¹ R³ 418 R¹ R⁴¹ R⁴ 419 R¹ R⁴¹ R⁵ 420 R¹ R⁴¹ R⁶ 421 R¹ R⁴¹ R⁷ 422 R¹ R⁴¹ R⁸ 423 R¹ R⁴¹ R⁹ 424 R¹ R⁴¹ R¹⁰ 425 R¹ R⁴¹ R¹¹ 426 R¹ R⁴¹ R¹² 427 R¹ R⁴¹ R¹³ 428 R¹ R⁴¹ R¹⁴ 429 R¹ R⁴¹ R¹⁵ 430 R¹ R⁴¹ R¹⁶ 431 R¹ R⁴¹ R¹⁷ 432 R¹ R⁴¹ R¹⁸ 433 R¹ R⁴¹ R¹⁹ 434 R¹ R⁴¹ R²⁰ 435 R¹ R⁴¹ R²¹ 436 R¹ R⁴¹ R²² 437 R¹ R⁴¹ R²³ 438 R¹ R⁴¹ R²⁴ 439 R¹ R⁴¹ R²⁵ 440 R¹ R⁴¹ R²⁶ 441 R¹ R⁴¹ R²⁷ 442 R¹ R⁴¹ R²⁸ 443 R¹ R⁴¹ R²⁹ 444 R¹ R⁴¹ R³⁰ 445 R¹ R⁴¹ R³¹ 446 R¹ R⁴¹ R³² 447 R¹ R⁴¹ R³³ 448 R¹ R⁴¹ R³⁴ 449 R¹ R⁴¹ R³⁵ 450 R¹ R⁴¹ R³⁶ 451 R¹ R⁴¹ R³⁷ 452 R¹ R⁴¹ R³⁸ 453 R¹ R⁴¹ R³⁹ 454 R¹ R⁴¹ R⁴⁰ 455 R¹ R⁴¹ R⁴¹ 456 R¹ R⁴¹ R⁴² 457 R¹ R⁴¹ R⁴³ 458 R¹ R⁴¹ R⁴⁴ 459 R¹ R⁴¹ R⁴⁵ 460 R¹ R⁴¹ R⁴⁶ 461 R¹ R⁴¹ R⁴⁷ 462 R¹ R⁴¹ R⁴⁸ 463 R¹ R⁴¹ R⁴⁹ 464 R¹ R⁴¹ R⁵⁰ 465 R¹ R⁴¹ R⁵¹ 466 R¹ R⁴¹ R⁵² 467 R¹ R⁴¹ R⁵³ 468 R¹ R⁴¹ R⁵⁴ 469 R¹ R⁴¹ R⁵⁵ 470 R¹ R⁴¹ R⁵⁶ 471 R¹ R⁴¹ R⁵⁷ 472 R¹ R⁴¹ R⁵⁸ 473 R¹ R⁴¹ R⁵⁹ 474 R¹ R⁴¹ R⁶⁰ 475 R¹ R⁴¹ R⁶¹ 476 R¹ R⁴¹ R⁶² 477 R¹ R⁴¹ R⁶³ 478 R¹ R⁴¹ R⁶⁴ 479 R¹ R⁴¹ R⁶⁵ 480 R¹ R⁴¹ R⁶⁶ 481 R¹ R⁴¹ R⁶⁷ 482 R¹ R⁴¹ R⁶⁸ 483 R¹ R⁴¹ R⁶⁹ 484 R² R¹ R¹ 485 R² R¹ R² 486 R² R¹ R³ 487 R² R¹ R⁴ 488 R² R¹ R⁵ 489 R² R¹ R⁶ 490 R² R¹ R⁷ 491 R² R¹ R⁸ 492 R² R¹ R⁹ 493 R² R¹ R¹⁰ 494 R² R¹ R¹¹ 495 R² R¹ R¹² 496 R² R¹ R¹³ 497 R² R¹ R¹⁴ 498 R² R¹ R¹⁵ 499 R² R¹ R¹⁶ 500 R² R¹ R¹⁷ 501 R² R¹ R¹⁸ 502 R² R¹ R¹⁹ 503 R² R¹ R²⁰ 504 R² R¹ R²¹ 505 R² R¹ R²² 506 R² R¹ R²³ 507 R² R¹ R²⁴ 508 R² R¹ R²⁵ 509 R² R¹ R²⁶ 510 R² R¹ R²⁷ 511 R² R¹ R²⁸ 512 R² R¹ R²⁹ 513 R² R¹ R³⁰ 514 R² R¹ R³¹ 515 R² R¹ R³² 516 R² R¹ R³³ 517 R² R¹ R³⁴ 518 R² R¹ R³⁵ 519 R² R¹ R³⁶ 520 R² R¹ R³⁷ 521 R² R¹ R³⁸ 522 R² R¹ R³⁹ 523 R² R¹ R⁴⁰ 524 R² R¹ R⁴¹ 525 R² R¹ R⁴² 526 R² R¹ R⁴³ 527 R² R¹ R⁴⁴ 528 R² R¹ R⁴⁵ 529 R² R¹ R⁴⁶ 530 R² R¹ R⁴⁷ 531 R² R¹ R⁴⁸ 532 R² R¹ R⁴⁹ 533 R² R¹ R⁵⁰ 534 R² R¹ R⁵¹ 535 R² R¹ R⁵² 536 R² R¹ R⁵³ 537 R² R¹ R⁵⁴ 538 R² R¹ R⁵⁵ 539 R² R¹ R⁵⁶ 540 R² R¹ R⁵⁷ 541 R² R¹ R⁵⁸ 542 R² R¹ R⁵⁹ 543 R² R¹ R⁶⁰ 544 R² R¹ R⁶¹ 545 R² R¹ R⁶² 546 R² R¹ R⁶³ 547 R² R¹ R⁶⁴ 548 R² R¹ R⁶⁵ 549 R² R¹ R⁶⁶ 550 R² R¹ R⁶⁷ 551 R² R¹ R⁶⁸ 552 R² R¹ R⁶⁹ 553 R² R² R¹ 554 R² R² R² 555 R² R² R³ 556 R² R² R⁴ 557 R² R² R⁵ 558 R² R² R⁶ 559 R² R² R⁷ 560 R² R² R⁸ 561 R² R² R⁹ 562 R² R² R¹⁰ 563 R² R² R¹¹ 564 R² R² R¹² 565 R² R² R¹³ 566 R² R² R¹⁴ 567 R² R² R¹⁵ 568 R² R² R¹⁶ 569 R² R² R¹⁷ 570 R² R² R¹⁸ 571 R² R² R¹⁹ 572 R² R² R²⁰ 573 R² R² R²¹ 574 R² R² R²² 575 R² R² R²³ 576 R² R² R²⁴ 577 R² R² R²⁵ 578 R² R² R²⁶ 579 R² R² R²⁷ 580 R² R² R²⁸ 581 R² R² R²⁹ 582 R² R² R³⁰ 583 R² R² R³¹ 584 R² R² R³² 585 R² R² R³³ 586 R² R² R³⁴ 587 R² R² R³⁵ 588 R² R² R³⁶ 589 R² R² R³⁷ 590 R² R² R³⁸ 591 R² R² R³⁹ 592 R² R² R⁴⁰ 593 R² R² R⁴¹ 594 R² R² R⁴² 595 R² R² R⁴³ 596 R² R² R⁴⁴ 597 R² R² R⁴⁵ 598 R² R² R⁴⁶ 599 R² R² R⁴⁷ 600 R² R² R⁴⁸ 601 R² R² R⁴⁹ 602 R² R² R⁵⁰ 603 R² R² R⁵¹ 604 R² R² R⁵² 605 R² R² R⁵³ 606 R² R² R⁵⁴ 607 R² R² R⁵⁵ 608 R² R² R⁵⁶ 609 R² R² R⁵⁷ 610 R² R² R⁵⁸ 611 R² R² R⁵⁹ 612 R² R² R⁶⁰ 613 R² R² R⁶¹ 614 R² R² R⁶² 615 R² R² R⁶³ 616 R² R² R⁶⁴ 617 R² R² R⁶⁵ 618 R² R² R⁶⁶ 619 R² R² R⁶⁷ 620 R² R² R⁶⁸ 621 R² R² R⁶⁹ 622 R² R⁷ R¹ 623 R² R² R² 624 R² R³ R³ 625 R² R⁴ R⁴ 626 R² R⁵ R⁵ 627 R² R⁶ R⁶ 628 R² R⁷ R⁷ 629 R² R⁷ R⁸ 630 R² R⁷ R⁹ 631 R² R⁷ R¹⁰ 632 R² R⁷ R¹¹ 633 R² R⁷ R¹² 634 R² R⁷ R¹³ 635 R² R⁷ R¹⁴ 636 R² R⁷ R¹⁵ 637 R² R⁷ R¹⁶ 638 R² R⁷ R¹⁷ 639 R² R⁷ R¹⁸ 640 R² R⁷ R¹⁹ 641 R² R⁷ R²⁰ 642 R² R⁷ R²¹ 643 R² R⁷ R²² 644 R² R⁷ R²³ 645 R² R⁷ R²⁴ 646 R² R⁷ R²⁵ 647 R² R⁷ R²⁶ 648 R² R⁷ R²⁷ 649 R² R⁷ R²⁸ 650 R² R⁷ R²⁹ 651 R² R⁷ R³⁰ 652 R² R⁷ R³¹ 653 R² R⁷ R³² 654 R² R⁷ R³³ 655 R² R⁷ R³⁴ 656 R² R⁷ R³⁵ 657 R² R⁷ R³⁶ 658 R² R⁷ R³⁷ 659 R² R⁷ R³⁸ 660 R² R⁷ R³⁹ 661 R² R⁷ R⁴⁰ 662 R² R⁷ R⁴¹ 663 R² R⁷ R⁴² 664 R² R⁷ R⁴³ 665 R² R⁷ R⁴⁴ 666 R² R⁷ R⁴⁵ 667 R² R⁷ R⁴⁶ 668 R² R⁷ R⁴⁷ 669 R² R⁷ R⁴⁸ 670 R² R⁷ R⁴⁹ 671 R² R⁷ R⁵⁰ 672 R² R⁷ R⁵¹ 673 R² R⁷ R⁵² 674 R² R⁷ R⁵³ 675 R² R⁷ R⁵⁴ 676 R² R⁷ R⁵⁵ 677 R² R⁷ R⁵⁶ 678 R² R⁷ R⁵⁷ 679 R² R⁷ R⁵⁸ 680 R² R⁷ R⁵⁹ 681 R² R⁷ R⁶⁰ 682 R² R⁷ R⁶¹ 683 R² R⁷ R⁶² 684 R² R⁷ R⁶³ 685 R² R⁷ R⁶⁴ 686 R² R⁷ R⁶⁵ 687 R² R⁷ R⁶⁶ 688 R² R⁷ R⁶⁷ 689 R² R⁷ R⁶⁸ 690 R² R⁷ R⁶⁹ 691 R² R¹⁴ R¹ 692 R² R¹⁴ R² 693 R² R¹⁴ R³ 694 R² R¹⁴ R⁴ 695 R² R¹⁴ R⁵ 696 R² R¹⁴ R⁶ 697 R² R¹⁴ R⁷ 698 R² R¹⁴ R⁸ 699 R² R¹⁴ R⁹ 700 R² R¹⁴ R¹⁰ 701 R² R¹⁴ R¹¹ 702 R² R¹⁴ R¹² 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R² R³² R¹¹ 771 R² R³² R¹² 772 R² R³² R¹³ 773 R² R³² R¹⁴ 774 R² R³² R¹⁵ 775 R² R³² R¹⁶ 776 R² R³² R¹⁷ 777 R² R³² R¹⁸ 778 R² R³² R¹⁹ 779 R² R³² R²⁰ 780 R² R³² R²¹ 781 R² R³² R²² 782 R² R³² R²³ 783 R² R³² R²⁴ 784 R² R³² R²⁵ 785 R² R³² R²⁶ 786 R² R³² R²⁷ 787 R² R³² R²⁸ 788 R² R³² R²⁹ 789 R² R³² R³⁰ 790 R² R³² R³¹ 791 R² R³² R³² 792 R² R³² R³³ 793 R² R³² R³⁴ 794 R² R³² R³⁵ 795 R² R³² R³⁶ 796 R² R³² R³⁷ 797 R² R³² R³⁸ 798 R² R³² R³⁹ 799 R² R³² R⁴⁰ 800 R² R³² R⁴¹ 801 R² R³² R⁴² 802 R² R³² R⁴³ 803 R² R³² R⁴⁴ 804 R² R³² R⁴⁵ 805 R² R³² R⁴⁶ 806 R² R³² R⁴⁷ 807 R² R³² R⁴⁸ 808 R² R³² R⁴⁹ 809 R² R³² R⁵⁰ 810 R² R³² R⁵¹ 811 R² R³² R⁵² 812 R² R³² R⁵³ 813 R² R³² R⁵⁴ 814 R² R³² R⁵⁵ 815 R² R³² R⁵⁶ 816 R² R³² R⁵⁷ 817 R² R³² R⁵⁸ 818 R² R³² R⁵⁹ 819 R² R³² R⁶⁰ 820 R² R³² R⁶¹ 821 R² R³² R⁶² 822 R² R³² R⁶³ 823 R² R³² R⁶⁴ 824 R² R³² R⁶⁵ 825 R² R³² R⁶⁶ 826 R² R³² R⁶⁷ 827 R² R³² R⁶⁸ 828 R² R³² R⁶⁹ 829 R² R³⁶ R¹ 830 R² R³⁶ R² 831 R² R³⁶ R³ 832 R² R³⁶ R⁴ 833 R² R³⁶ R⁵ 834 R² R³⁶ R⁶ 835 R² R³⁶ R⁷ 836 R² R³⁶ R⁸ 837 R² R³⁶ R⁹ 838 R² R³⁶ R¹⁰ 839 R² R³⁶ R¹¹ 840 R² R³⁶ R¹² 841 R² R³⁶ R¹³ 842 R² R³⁶ R¹⁴ 843 R² R³⁶ R¹⁵ 844 R² R³⁶ R¹⁶ 845 R² R³⁶ R¹⁷ 846 R² R³⁶ R¹⁸ 847 R² R³⁶ R¹⁹ 848 R² R³⁶ R²⁰ 849 R² R³⁶ R²¹ 850 R² R³⁶ R²² 851 R² R³⁶ R²³ 852 R² R³⁶ R²⁴ 853 R² R³⁶ R²⁵ 854 R² R³⁶ R²⁶ 855 R² R³⁶ R²⁷ 856 R² R³⁶ R²⁸ 857 R² R³⁶ R²⁹ 858 R² R³⁶ R³⁰ 859 R² R³⁶ R³¹ 860 R² R³⁶ R³² 861 R² R³⁶ R³³ 862 R² R³⁶ R³⁴ 863 R² R³⁶ R³⁵ 864 R² R³⁶ R³⁶ 865 R² R³⁶ R³⁷ 866 R² R³⁶ R³⁸ 867 R² R³⁶ R³⁹ 868 R² R³⁶ R⁴⁰ 869 R² R³⁶ R⁴¹ 870 R² R³⁶ R⁴² 871 R² R³⁶ R⁴³ 872 R² R³⁶ R⁴⁴ 873 R² R³⁶ R⁴⁵ 874 R² R³⁶ R⁴⁶ 875 R² R³⁶ R⁴⁷ 876 R² R³⁶ R⁴⁸ 877 R² R³⁶ R⁴⁹ 878 R² R³⁶ R⁵⁰ 879 R² R³⁶ R⁵¹ 880 R² R³⁶ R⁵² 881 R² R³⁶ R⁵³ 882 R² R³⁶ R⁵⁴ 883 R² R³⁶ R⁵⁵ 884 R² R³⁶ R⁵⁶ 885 R² R³⁶ R⁵⁷ 886 R² R³⁶ R⁵⁸ 887 R² R³⁶ R⁵⁹ 888 R² R³⁶ R⁶⁰ 889 R² R³⁶ R⁶¹ 890 R² R³⁶ R⁶² 891 R² R³⁶ R⁶³ 892 R² R³⁶ R⁶⁴ 893 R² R³⁶ R⁶⁵ 894 R² R³⁶ R⁶⁶ 895 R² R³⁶ R⁶⁷ 896 R² R³⁶ R⁶⁸ 897 R² R³⁶ R⁶⁹ 898 R² R⁴¹ R¹ 899 R² R⁴¹ R² 900 R² R⁴¹ R³ 901 R² R⁴¹ R⁴ 902 R² R⁴¹ R⁵ 903 R² R⁴¹ R⁶ 904 R² R⁴¹ R⁷ 905 R² R⁴¹ R⁸ 906 R² R⁴¹ R⁹ 907 R² R⁴¹ R¹⁰ 908 R² R⁴¹ R¹¹ 909 R² R⁴¹ R¹² 910 R² R⁴¹ R¹³ 911 R² R⁴¹ R¹⁴ 912 R² R⁴¹ R¹⁵ 913 R² R⁴¹ R¹⁶ 914 R² R⁴¹ R¹⁷ 915 R² R⁴¹ R¹⁸ 916 R² R⁴¹ R¹⁹ 917 R² R⁴¹ R²⁰ 918 R² R⁴¹ R²¹ 919 R² R⁴¹ R²² 920 R² R⁴¹ R²³ 921 R² R⁴¹ R²⁴ 922 R² R⁴¹ R²⁵ 923 R² R⁴¹ R²⁶ 924 R² R⁴¹ R²⁷ 925 R² R⁴¹ R²⁸ 926 R² R⁴¹ R²⁹ 927 R² R⁴¹ R³⁰ 928 R² R⁴¹ R³¹ 929 R² R⁴¹ R³² 930 R² R⁴¹ R³³ 931 R² R⁴¹ R³⁴ 932 R² R⁴¹ R³⁵ 933 R² R⁴¹ R³⁶ 934 R² R⁴¹ R³⁷ 935 R² R⁴¹ R³⁸ 936 R² R⁴¹ R³⁹ 937 R² R⁴¹ R⁴⁰ 938 R² R⁴¹ R⁴¹ 939 R² R⁴¹ R⁴² 940 R² R⁴¹ R⁴³ 941 R² R⁴¹ R⁴⁴ 942 R² R⁴¹ R⁴⁵ 943 R² R⁴¹ R⁴⁶ 944 R² R⁴¹ R⁴⁷ 945 R² R⁴¹ R⁴⁸ 946 R² R⁴¹ R⁴⁹ 947 R² R⁴¹ R⁵⁰ 948 R² R⁴¹ R⁵¹ 949 R² R⁴¹ R⁵² 950 R² R⁴¹ R⁵³ 951 R² R⁴¹ R⁵⁴ 952 R² R⁴¹ R⁵⁵ 953 R² R⁴¹ R⁵⁶ 954 R² R⁴¹ R⁵⁷ 955 R² R⁴¹ R⁵⁸ 956 R² R⁴¹ R⁵⁹ 957 R² R⁴¹ R⁶⁰ 958 R² R⁴¹ R⁶¹ 959 R² R⁴¹ R⁶² 960 R² R⁴¹ R⁶³ 961 R² R⁴¹ R⁶⁴ 962 R² R⁴¹ R⁶⁵ 963 R² R⁴¹ R⁶⁶ 964 R² R⁴¹ R⁶⁷ 965 R² R⁴¹ R⁶⁸ 966 R² R⁴¹ R⁶⁹ 967 R³² R¹ R¹ 968 R³² R¹ R² 969 R³² R¹ R³ 970 R³² R¹ R⁴ 971 R³² R¹ R⁵ 972 R³² R¹ R⁶ 973 R³² R¹ R⁷ 974 R³² R¹ R⁸ 975 R³² R¹ R⁹ 976 R³² R¹ R¹⁰ 977 R³² R¹ R¹¹ 978 R³² R¹ R¹² 979 R³² R¹ R¹³ 980 R³² R¹ R¹⁴ 981 R³² R¹ R¹⁵ 982 R³² R¹ R¹⁶ 983 R³² R¹ R¹⁷ 984 R³² R¹ R¹⁸ 985 R³² R¹ R¹⁹ 986 R³² R¹ R²⁰ 987 R³² R¹ R²¹ 988 R³² R¹ R²² 989 R³² R¹ R²³ 990 R³² R¹ R²⁴ 991 R³² R¹ R²⁵ 992 R³² R¹ R²⁶ 993 R³² R¹ R²⁷ 994 R³² R¹ R²⁸ 995 R³² R¹ R²⁹ 996 R³² R¹ R³⁰ 997 R³² R¹ R³¹ 998 R³² R¹ R³² 999 R³² R¹ R³³ 1000 R³² R¹ R³⁴ 1001 R³² R¹ R³⁵ 1002 R³² R¹ R³⁶ 1003 R³² R¹ R³⁷ 1004 R³² R¹ R³⁸ 1005 R³² R¹ R³⁹ 1006 R³² R¹ R⁴⁰ 1007 R³² R¹ R⁴¹ 1008 R³² R¹ R⁴² 1009 R³² R¹ R⁴³ 1010 R³² R¹ R⁴⁴ 1011 R³² R¹ R⁴⁵ 1012 R³² R¹ R⁴⁶ 1013 R³² R¹ R⁴⁷ 1014 R³² R¹ R⁴⁸ 1015 R³² R¹ R⁴⁹ 1016 R³² R¹ R⁵⁰ 1017 R³² R¹ R⁵¹ 1018 R³² R¹ R⁵² 1019 R³² R¹ R⁵³ 1020 R³² R¹ R⁵⁴ 1021 R³² R¹ R⁵⁵ 1022 R³² R¹ R⁵⁶ 1023 R³² R¹ R⁵⁷ 1024 R³² R¹ R⁵⁸ 1025 R³² R¹ R⁵⁹ 1026 R³² R¹ R⁶⁰ 1027 R³² R¹ R⁶¹ 1028 R³² R¹ R⁶² 1029 R³² R¹ R⁶³ 1030 R³² R¹ R⁶⁴ 1031 R³² R¹ R⁶⁵ 1032 R³² R¹ R⁶⁶ 1033 R³² R¹ R⁶⁷ 1034 R³² R¹ R⁶⁸ 1035 R³² R¹ R⁶⁹ 1036 R³² R² R¹ 1037 R³² R² R² 1038 R³² R² R³ 1039 R³² R² R⁴ 1040 R³² R² R⁵ 1041 R³² R² R⁶ 1042 R³² R² R⁷ 1043 R³² R² R⁸ 1044 R³² R² R⁹ 1045 R³² R² R¹⁰ 1046 R³² R² R¹¹ 1047 R³² R² R¹² 1048 R³² R² R¹³ 1049 R³² R² R¹⁴ 1050 R³² R² R¹⁵ 1051 R³² R² R¹⁶ 1052 R³² R² R¹⁷ 1053 R³² R² R¹⁸ 1054 R³² R² R¹⁹ 1055 R³² R² R²⁰ 1056 R³² R² R²¹ 1057 R³² R² R²² 1058 R³² R² R²³ 1059 R³² R² R²⁴ 1060 R³² R² R²⁵ 1061 R³² R² R²⁶ 1062 R³² R² R²⁷ 1063 R³² R² R²⁸ 1064 R³² R² R²⁹ 1065 R³² R² R³⁰ 1066 R³² R² R³¹ 1067 R³² R² R³² 1068 R³² R² R³³ 1069 R³² R² R³⁴ 1070 R³² R² R³⁵ 1071 R³² R² R³⁶ 1072 R³² R² R³⁷ 1073 R³² R² R³⁸ 1074 R³² R² R³⁹ 1075 R³² R² R⁴⁰ 1076 R³² R² R⁴¹ 1077 R³² R² R⁴² 1078 R³² R² R⁴³ 1079 R³² R² R⁴⁴ 1080 R³² R² R⁴⁵ 1081 R³² R² R⁴⁶ 1082 R³² R² R⁴⁷ 1083 R³² R² R⁴⁸ 1084 R³² R² R⁴⁹ 1085 R³² R² R⁵⁰ 1086 R³² R² R⁵¹ 1087 R³² R² R⁵² 1088 R³² R² R⁵³ 1089 R³² R² R⁵⁴ 1090 R³² R² R⁵⁵ 1091 R³² R² R⁵⁶ 1092 R³² R² R⁵⁷ 1093 R³² R² R⁵⁸ 1094 R³² R² R⁵⁹ 1095 R³² R² R⁶⁰ 1096 R³² R² R⁶¹ 1097 R³² R² R⁶² 1098 R³² R² R⁶³ 1099 R³² R² R⁶⁴ 1100 R³² R² R⁶⁵ 1101 R³² R² R⁶⁶ 1102 R³² R² R⁶⁷ 1103 R³² R² R⁶⁸ 1104 R³² R² R⁶⁹ 1105 R³² R⁷ R¹ 1106 R³² R⁷ R² 1107 R³² R⁷ R³ 1108 R³² R⁷ R⁴ 1109 R³² R⁷ R⁵ 1110 R³² R⁷ R⁶ 1111 R³² R⁷ R⁷ 1112 R³² R⁷ R⁸ 1113 R³² R⁷ R⁹ 1114 R³² R⁷ R¹⁰ 1115 R³² R⁷ R¹¹ 1116 R³² R⁷ R¹² 1117 R³² R⁷ R¹³ 1118 R³² R⁷ R¹⁴ 1119 R³² R⁷ R¹⁵ 1120 R³² R⁷ R¹⁶ 1121 R³² R⁷ R¹⁷ 1122 R³² R⁷ R¹⁸ 1123 R³² R⁷ R¹⁹ 1124 R³² R⁷ R²⁰ 1125 R³² R⁷ R²¹ 1126 R³² R⁷ R²² 1127 R³² R⁷ R²³ 1128 R³² R⁷ R²⁴ 1129 R³² R⁷ R²⁵ 1130 R³² R⁷ R²⁶ 1131 R³² R⁷ R²⁷ 1132 R³² R⁷ R²⁸ 1133 R³² R⁷ R²⁹ 1134 R³² R⁷ R³⁰ 1135 R³² R⁷ R³¹ 1136 R³² R⁷ R³² 1137 R³² R⁷ R³³ 1138 R³² R⁷ R³⁴ 1139 R³² R⁷ R³⁵ 1140 R³² R⁷ R³⁶ 1141 R³² R⁷ R³⁷ 1142 R³² R⁷ R³⁸ 1143 R³² R⁷ R³⁹ 1144 R³² R⁷ R⁴⁰ 1145 R³² R⁷ R⁴¹ 1146 R³² R⁷ R⁴² 1147 R³² R⁷ R⁴³ 1148 R³² R⁷ R⁴⁴ 1149 R³² R⁷ R⁴⁵ 1150 R³² R⁷ R⁴⁶ 1151 R³² R⁷ R⁴⁷ 1152 R³² R⁷ R⁴⁸ 1153 R³² R⁷ R⁴⁹ 1154 R³² R⁷ R⁵⁰ 1155 R³² R⁷ R⁵¹ 1156 R³² R⁷ R⁵² 1157 R³² R⁷ R⁵³ 1158 R³² R⁷ R⁵⁴ 1159 R³² R⁷ R⁵⁵ 1160 R³² R⁷ R⁵⁶ 1161 R³² R⁷ R⁵⁷ 1162 R³² R⁷ R⁵⁸ 1163 R³² R⁷ R⁵⁹ 1164 R³² R⁷ R⁶⁰ 1165 R³² R⁷ R⁶¹ 1166 R³² R⁷ R⁶² 1167 R³² R⁷ R⁶³ 1168 R³² R⁷ R⁶⁴ 1169 R³² R⁷ R⁶⁵ 1170 R³² R⁷ R⁶⁶ 1171 R³² R⁷ R⁶⁷ 1172 R³² R⁷ R⁶⁸ 1173 R³² R⁷ R⁶⁹ 1174 R³² R¹⁴ R¹ 1175 R³² R¹⁴ R² 1176 R³² R¹⁴ R³ 1177 R³² R¹⁴ R⁴ 1178 R³² R¹⁴ R⁵ 1179 R³² R¹⁴ R⁶ 1180 R³² R¹⁴ R⁷ 1181 R³² R¹⁴ R⁸ 1182 R³² R¹⁴ R⁹ 1183 R³² R¹⁴ R¹⁰ 1184 R³² R¹⁴ R¹¹ 1185 R³² R¹⁴ R¹² 1186 R³² R¹⁴ R¹³ 1187 R³² R¹⁴ R¹⁴ 1188 R³² R¹⁴ R¹⁵ 1189 R³² R¹⁴ R¹⁶ 1190 R³² R¹⁴ R¹⁷ 1191 R³² R¹⁴ R¹⁸ 1192 R³² R¹⁴ R¹⁹ 1193 R³² R¹⁴ R²⁰ 1194 R³² R¹⁴ R²¹ 1195 R³² R¹⁴ R²² 1196 R³² R¹⁴ R²³ 1197 R³² R¹⁴ R²⁴ 1198 R³² R¹⁴ R²⁵ 1199 R³² R¹⁴ R²⁶ 1200 R³² R¹⁴ R²⁷ 1201 R³² R¹⁴ R²⁸ 1202 R³² R¹⁴ R²⁹ 1203 R³² R¹⁴ R³⁰ 1204 R³² R¹⁴ R³¹ 1205 R³² R¹⁴ R³² 1206 R³² R¹⁴ R³³ 1207 R³² R¹⁴ R³⁴ 1208 R³² R¹⁴ R³⁵ 1209 R³² R¹⁴ R³⁶ 1210 R³² R¹⁴ R³⁷ 1211 R³² R¹⁴ R³⁸ 1212 R³² R¹⁴ R³⁹ 1213 R³² R¹⁴ R⁴⁰ 1214 R³² R¹⁴ R⁴¹ 1215 R³² R¹⁴ R⁴² 1216 R³² R¹⁴ R⁴³ 1217 R³² R¹⁴ R⁴⁴ 1218 R³² R¹⁴ R⁴⁵ 1219 R³² R¹⁴ R⁴⁶ 1220 R³² R¹⁴ R⁴⁷ 1221 R³² R¹⁴ R⁴⁸ 1222 R³² R¹⁴ R⁴⁹ 1223 R³² R¹⁴ R⁵⁰ 1224 R³² R¹⁴ R⁵¹ 1225 R³² R¹⁴ R⁵² 1226 R³² R¹⁴ R⁵³ 1227 R³² R¹⁴ R⁵⁴ 1228 R³² R¹⁴ R⁵⁵ 1229 R³² R¹⁴ R⁵⁶ 1230 R³² R¹⁴ R⁵⁷ 1231 R³² R¹⁴ R⁵⁸ 1232 R³² R¹⁴ R⁵⁹ 1233 R³² R¹⁴ R⁶⁰ 1234 R³² R¹⁴ R⁶¹ 1235 R³² R¹⁴ R⁶² 1236 R³² R¹⁴ R⁶³ 1237 R³² R¹⁴ R⁶⁴ 1238 R³² R¹⁴ R⁶⁵ 1239 R³² R¹⁴ R⁶⁶ 1240 R³² R¹⁴ R⁶⁷ 1241 R³² R¹⁴ R⁶⁸ 1242 R³² R¹⁴ R⁶⁹ 1243 R³² R³² R¹ 1244 R³² R³² R² 1245 R³² R³² R³ 1246 R³² R³² R⁴ 1247 R³² R³² R⁵ 1248 R³² R³² R⁶ 1249 R³² R³² R⁷ 1250 R³² R³² R⁸ 1251 R³² R³² R⁹ 1252 R³² R³² R¹⁰ 1253 R³² R³² R¹¹ 1254 R³² R³² R¹² 1255 R³² R³² R¹³ 1256 R³² R³² R¹⁴ 1257 R³² R³² R¹⁵ 1258 R³² R³² R¹⁶ 1259 R³² R³² R¹⁷ 1260 R³² R³² R¹⁸ 1261 R³² R³² R¹⁹ 1262 R³² R³² R²⁰ 1263 R³² R³² R²¹ 1264 R³² R³² R²² 1265 R³² R³² R²³ 1266 R³² R³² R²⁴ 1267 R³² R³² R²⁵ 1268 R³² R³² R²⁶ 1269 R³² R³² R²⁷ 1270 R³² R³² R²⁸ 1271 R³² R³² R²⁹ 1272 R³² R³² R³⁰ 1273 R³² R³² R³¹ 1274 R³² R³² R³² 1275 R³² R³² R³³ 1276 R³² R³² R³⁴ 1277 R³² R³² R³⁵ 1278 R³² R³² R³⁶ 1279 R³² R³² R³⁷ 1280 R³² R³² R³⁸ 1281 R³² R³² R³⁹ 1282 R³² R³² R⁴⁰ 1283 R³² R³² R⁴¹ 1284 R³² R³² R⁴² 1285 R³² R³² R⁴³ 1286 R³² R³² R⁴⁴ 1287 R³² R³² R⁴⁵ 1288 R³² R³² R⁴⁶ 1289 R³² R³² R⁴⁷ 1290 R³² R³² R⁴⁸ 1291 R³² R³² R⁴⁹ 1292 R³² R³² R⁵⁰ 1293 R³² R³² R⁵¹ 1294 R³² R³² R⁵² 1295 R³² R³² R⁵³ 1296 R³² R³² R⁵⁴ 1297 R³² R³² R⁵⁵ 1298 R³² R³² R⁵⁶ 1299 R³² R³² R⁵⁷ 1300 R³² R³² R⁵⁸ 1301 R³² R³² R⁵⁹ 1302 R³² R³² R⁶⁰ 1303 R³² R³² R⁶¹ 1304 R³² R³² R⁶² 1305 R³² R³² R⁶³ 1306 R³² R³² R⁶⁴ 1307 R³² R³² R⁶⁵ 1308 R³² R³² R⁶⁶ 1309 R³² R³² R⁶⁷ 1310 R³² R³² R⁶⁸ 1311 R³² R³² R⁶⁹ 1312 R³² R³⁶ R¹ 1313 R³² R³⁶ R² 1314 R³² R³⁶ R³ 1315 R³² R³⁶ R⁴ 1316 R³² R³⁶ R⁵ 1317 R³² R³⁶ R⁶ 1318 R³² R³⁶ R⁷ 1319 R³² R³⁶ R⁸ 1320 R³² R³⁶ R⁹ 1321 R³² R³⁶ R¹⁰ 1322 R³² R³⁶ R¹¹ 1323 R³² R³⁶ R¹² 1324 R³² R³⁶ R¹³ 1325 R³² R³⁶ R¹⁴ 1326 R³² R³⁶ R¹⁵ 1327 R³² R³⁶ R¹⁶ 1328 R³² R³⁶ R¹⁷ 1329 R³² R³⁶ R¹⁸ 1330 R³² R³⁶ R¹⁹ 1331 R³² R³⁶ R²⁰ 1332 R³² R³⁶ R²¹ 1333 R³² R³⁶ R²² 1334 R³² R³⁶ R²³ 1335 R³² R³⁶ R²⁴ 1336 R³² R³⁶ R²⁵ 1337 R³² R³⁶ R²⁶ 1338 R³² R³⁶ R²⁷ 1339 R³² R³⁶ R²⁸ 1340 R³² R³⁶ R²⁹ 1341 R³² R³⁶ R³⁰ 1342 R³² R³⁶ R³¹ 1343 R³² R³⁶ R³² 1344 R³² R³⁶ R³³ 1345 R³² R³⁶ R³⁴ 1346 R³² R³⁶ R³⁵ 1347 R³² R³⁶ R³⁶ 1348 R³² R³⁶ R³⁷ 1349 R³² R³⁶ R³⁸ 1350 R³² R³⁶ R³⁹ 1351 R³² R³⁶ R⁴⁰ 1352 R³² R³⁶ R⁴¹ 1353 R³² R³⁶ R⁴² 1354 R³² R³⁶ R⁴³ 1355 R³² R³⁶ R⁴⁴ 1356 R³² R³⁶ R⁴⁵ 1357 R³² R³⁶ R⁴⁶ 1358 R³² R³⁶ R⁴⁷ 1359 R³² R³⁶ R⁴⁸ 1360 R³² R³⁶ R⁴⁹ 1361 R³² R³⁶ R⁵⁰ 1362 R³² R³⁶ R⁵¹ 1363 R³² R³⁶ R⁵² 1364 R³² R³⁶ R⁵³ 1365 R³² R³⁶ R⁵⁴ 1366 R³² R³⁶ R⁵⁵ 1367 R³² R³⁶ R⁵⁶ 1368 R³² R³⁶ R⁵⁷ 1369 R³² R³⁶ R⁵⁸ 1370 R³² R³⁶ R⁵⁹ 1371 R³² R³⁶ R⁶⁰ 1372 R³² R³⁶ R⁶¹ 1373 R³² R³⁶ R⁶² 1374 R³² R³⁶ R⁶³ 1375 R³² R³⁶ R⁶⁴ 1376 R³² R³⁶ R⁶⁵ 1377 R³² R³⁶ R⁶⁶ 1378 R³² R³⁶ R⁶⁷ 1379 R³² R³⁶ R⁶⁸ 1380 R³² R³⁶ R⁶⁹ 1381 R³² R⁴¹ R¹ 1382 R³² R⁴¹ R² 1383 R³² R⁴¹ R³ 1384 R³² R⁴¹ R⁴ 1385 R³² R⁴¹ R⁵ 1386 R³² R⁴¹ R⁶ 1387 R³² R⁴¹ R⁷ 1388 R³² R⁴¹ R⁸ 1389 R³² R⁴¹ R⁹ 1390 R³² R⁴¹ R¹⁰ 1391 R³² R⁴¹ R¹¹ 1392 R³² R⁴¹ R¹² 1393 R³² R⁴¹ R¹³ 1394 R³² R⁴¹ R¹⁴ 1395 R³² R⁴¹ R¹⁵ 1396 R³² R⁴¹ R¹⁶ 1397 R³² R⁴¹ R¹⁷ 1398 R³² R⁴¹ R¹⁸ 1399 R³² R⁴¹ R¹⁹ 1400 R³² R⁴¹ R²⁰ 1401 R³² R⁴¹ R²¹ 1402 R³² R⁴¹ R²² 1403 R³² R⁴¹ R²³ 1404 R³² R⁴¹ R²⁴ 1405 R³² R⁴¹ R²⁵ 1406 R³² R⁴¹ R²⁶ 1407 R³² R⁴¹ R²⁷ 1408 R³² R⁴¹ R²⁸ 1409 R³² R⁴¹ R²⁹ 1410 R³² R⁴¹ R³⁰ 1411 R³² R⁴¹ R³¹ 1412 R³² R⁴¹ R³² 1413 R³² R⁴¹ R³³ 1414 R³² R⁴¹ R³⁴ 1415 R³² R⁴¹ R³⁵ 1416 R³² R⁴¹ R³⁶ 1417 R³² R⁴¹ R³⁷ 1418 R³² R⁴¹ R³⁸ 1419 R³² R⁴¹ R³⁹ 1420 R³² R⁴¹ R⁴⁰ 1421 R³² R⁴¹ R⁴¹ 1422 R³² R⁴¹ R⁴² 1423 R³² R⁴¹ R⁴³ 1424 R³² R⁴¹ R⁴⁴ 1425 R³² R⁴¹ R⁴⁵ 1426 R³² R⁴¹ R⁴⁶ 1427 R³² R⁴¹ R⁴⁷ 1428 R³² R⁴¹ R⁴⁸ 1429 R³² R⁴¹ R⁴⁹ 1430 R³² R⁴¹ R⁵⁰ 1431 R³² R⁴¹ R⁵¹ 1432 R³² R⁴¹ R⁵² 1433 R³² R⁴¹ R⁵³ 1434 R³² R⁴¹ R⁵⁴ 1435 R³² R⁴¹ R⁵⁵ 1436 R³² R⁴¹ R⁵⁶ 1437 R³² R⁴¹ R⁵⁷ 1438 R³² R⁴¹ R⁵⁸ 1439 R³² R⁴¹ R⁵⁹ 1440 R³² R⁴¹ R⁶⁰ 1441 R³² R⁴¹ R⁶¹ 1442 R³² R⁴¹ R⁶² 1443 R³² R⁴¹ R⁶³ 1444 R³² R⁴¹ R⁶⁴ 1445 R³² R⁴¹ R⁶⁵ 1446 R³² R⁴¹ R⁶⁶ 1447 R³² R⁴¹ R⁶⁷ 1448 R³² R⁴¹ R⁶⁸ 1449 R³² R⁴¹ R⁶⁹

wherein R¹ to R⁶⁹ have the following structures:


11. The compound of claim 2, wherein the compound has a formula of M(L_(A))_(x)(L_(B))_(y)(L_(C))_(z) wherein each one of L_(B) and L_(C) is a bidentate ligand; and wherein x is 1, 2, or 3; y is 0, 1, or 2; z is 0, 1, or 2; and x+y+z is the oxidation state of the metal M.
 12. The compound of claim 11, wherein the compound has a formula selected from the group consisting of Ir(L_(A))₃, Ir(L_(A))(L_(B))₂, Ir(L_(A))₂(L_(B)), Ir(L_(A))₂(L_(C)), and Ir(L_(A))(L_(B))(L_(C)); and wherein L_(A), L_(B), and L_(C) are different from each other; or the compound has a formula of Pt(L_(A))(L_(B)); and wherein L_(A) and L_(B) can be same or different.
 13. The compound of claim 11, wherein L_(B) and L_(C) are each independently selected from the group consisting of:

wherein each X¹ to X¹³ are independently selected from the group consisting of carbon and nitrogen; wherein X is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″; wherein R′ and R″ are optionally fused or joined to form a ring; wherein each R_(a), R_(b), R_(c), and R_(d) may represent from mono substitution to the possible maximum number of substitution, or no substitution; wherein R′, R″, R_(a), R_(b), R_(c), and R_(d) are each independently a hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; and wherein any two adjacent substitutents of R_(a), R_(b), R_(c), and R_(d) are optionally fused or joined to form a ring or form a multidentate ligand.
 14. The compound of claim 10, wherein the compound is selected from the group consisting of Ir(L_(X1-1))₃ to Ir(L_(X897-38))₃ with the general numbering formula Ir(L_(Xh-m))₃, Ir(L_(X1-39))₃ to Ir(L_(X1446-57))₃ with the general numbering formula Ir(L_(Xi-n))₃, Ir(L_(X1-1))(L_(B1))₂ to Ir(L_(X897-38))(L_(B263))₂ with the general numbering formula Ir(L_(Xh-m))(L_(Bk))₂, Ir(L_(X1-39))(L_(B1))₂ to Ir(L_(X1446-57))(L_(B263))₂ with the general numbering formula Ir(L_(Xi-n))(L_(Bk))₂; wherein k is an integer from 1 to 263; wherein L_(Bk) has the following structures:


15. The compound of claim 1, wherein the compound is selected from the group consisting of:


16. An organic light emitting device (OLED) comprising: an anode; a cathode; and an organic layer, disposed between the anode and the cathode, comprising a compound comprising a first ligand L_(X) of Formula II

herein, F is a 5-membered or 6-membered carbocyclic or heterocyclic ring; each R^(F) and R^(G) independently represents mono to the maximum possible number of substitutions, or no substitution; Z³ and Z⁴ are each independently C or N and coordinated to a metal M to form a 5-membered chelate ring; G is a fused ring structure comprising five or more fused heterocyclic or carbocyclic rings, of which at least one ring is of Formula III

the fused heterocyclic or carbocyclic rings in the fused ring structure G are 5-membered or 6-membered; of which if two or more 5-membered rings are present, at least two of the 5-membered rings are fused to one another; Y is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″; each R′, R″, R^(F), and R^(G) is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; the metal M can be coordinated to other ligands; and the ligand L_(X) can be linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand.
 17. The OLED of claim 16, wherein the organic layer is an emissive layer and the compound can be an emissive dopant or a non-emissive dopant.
 18. The OLED of claim 16, wherein the organic layer further comprises a host, wherein host contains at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
 19. The OLED of claim 18, wherein the host is selected from the group consisting of:

and combinations thereof.
 20. A consumer product comprising an organic light-emitting device (OLED) comprising: an anode; a cathode; and an organic layer, disposed between the anode and the cathode, comprising a compound comprising a first ligand L_(X) of Formula II

wherein, F is a 5-membered or 6-membered carbocyclic or heterocyclic ring; each R^(F) and R^(G) independently represents mono to the maximum possible number of substitutions, or no substitution; Z³ and Z⁴ are each independently C or N and coordinated to a metal M to form a 5-membered chelate ring; G is a fused ring structure comprising five or more fused heterocyclic or carbocyclic rings, of which at least one ring is of Formula III

the fused heterocyclic or carbocyclic rings in the fused ring structure G are 5-membered or 6-membered; of which if two or more 5-membered rings are present, at least two of the 5-membered rings are fused to one another; Y is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″; each R′, R″, R^(F), and R^(G) is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; the metal M can be coordinated to other ligands; and the ligand L_(X) can be linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand. 